Rheology control agents for coating compositions

ABSTRACT

The present invention is directed to a rheology control agent for coating compositions. The rheology control agent includes a compound having the Formula (II) including isomers or mixtures of isomers thereof: 
                         
wherein R, R 9 , R 10 , m and n are described in the specification. The coating compositions containing the rheology control agent have improved rheology control on application and are useful for OEM, refinishing or repainting the exterior of automobile and truck bodies and parts thereof.

PRIORITY

This application claims priority from U.S. Provisional PatentApplication Ser. No. 60/643,510, filed Jan. 13, 2005, incorporatedherein by reference.

BACKGROUND OF THE INVENTION

This invention relates to rheology control agents for solvent-borne andwater-borne coating compositions useful for finishing the exterior ofautomobiles and trucks, and in particular to liquid solvent-bornecoating compositions having improved rheology to facilitate sprayapplication.

DESCRIPTION OF THE PRIOR ART

The top coat finish of choice currently being used on automobiles andtrucks is a clear coat/color coat finish in which a clear coating isapplied over the pigmented color coat or base coat to provide protectionto the color coat and improve the appearance of the overall finishparticularly gloss and DOI (distinctness of image). Mono-coats ofpigmented finishes also are used without a clear coat on someautomobiles and trucks, in particular, older models. Primers,primer-surfacers and sealers for many automotive and truck applicationsare applied initially before one of the aforementioned top-coats areapplied. All of the above compositions when applied by conventionalspraying techniques, have rheology control problems, such as, runningand sagging after application. Top-coat finishes containing flakepigments or special effect pigments have problems with flake control andproper flake orientation for optimum appearance.

Additional problems are caused by many localities that have regulationsrequiring the use of low VOC (volatile organic content) coatingcompositions to reduce air pollution caused by organic solvent emissions

Typically, these low VOC coating compositions have a VOC of 2.1pounds/gallon (252 g/l) or less and when applied by conventional spraytechniques often have problems with running and sagging of the finishafter application and also problems with proper flake orientation andcontrol.

These low VOC coating compositions typically are used for OEM (originalequipment manufacture) of automobiles, trucks and parts thereof and forrefinishing or repainting of automobiles and trucks or parts thereof andare usually formulated using relatively low molecular weight polymers.However, as pointed out above, such compositions generally have poorrheology control and run and sag after spray application particularlywhen applied to vertical surfaces, such as, door panels and body sidepanels and have poor control of flake orientation. A rheology controlagent is needed to improve the rheology control of these coatingcompositions to prevent runs and sags after application and in generalto provide a finish with an acceptable appearance with good gloss andDOI.

Rheology control is also very critical for the low solids lacquerbasecoats typically used in the refinishing or repainting of automobilesand trucks. These lacquer basecoats are typically applied at very lowsolids, as low as 10% by volume, using spray application. To achieveadequate hiding in these coatings, a dry film thickness of around 15 to65 microns is typically required. Because of the very low volume solidsof these coatings, the applied wet film thickness of these coatings canbe around 350 microns or more. This requires the use of a very effectiverheology control agent to prevent sagging and to give good flakeorientation. Another aspect of these lacquer coatings, is that theytypically contain higher molecular weight binder components which can beincompatible with many conventional rheology control agents.

Rheology control agents are shown in U.S. Pat. No. 3,893,956, U.S. Pat.No. 4,311,622, U.S. Pat. No. 4,314,924, U.S. Pat. No. 4,677,028, U.S.Pat. No. 4,851,294, U.S. Pat. No. 6,420,466 B1, U.S. Pat. No. 6,617,468B2, and EP 0683214, EP 1162242, DE 10241853B3, and WO 03/037849. Theserheology control agents of the prior art in general cannot be formulatedinto high solids compositions and do not provide the necessary level ofoptical clarity to the resulting finishes and form finishes having lowDOI levels, particularly when the coating compositions are ambienttemperature curing compositions. Some of these rheology control agentshave to be prepared in the presence of the binder of the coatingcomposition to achieve the desired level of rheological control, whichadds to the manufacturing costs of the composition by requiringadditional manufacturing steps and the use of specific and alsoexpensive equipment. Also, some rheology control agents, for example,taught by U.S. Pat. No. 6,617,468 B2 limit the weatherability of theresulting finish, which over time, negatively impacts the appearance ofthe finish. Some rheology control agents, for example, taught by U.S.Pat. No. 4,311,622 are limited in their compatibility with the resinsystem. Furthermore, some rheology control agents, for example, taughtby U.S. Pat. No. 4,311,622 or WO 02/064684 show insufficientcompatibility in the resin system of choice especially rheology controlagents prepared using hydroxy functional monoamines.

U.S. Patent Publication 2002/0159961, published Oct. 31, 2002 showsgelling agents that are used to gel oils and in cosmetic compositions,such as, antiperspirants but have not been suggested for use in coatingcompositions.

Accordingly, there is still a need for coating compositions, bothsolvent-borne and water-borne, for a wide variety of application thatcontain a rheology control agent that will provide an acceptable levelof rheology control on application of the composition withoutdeteriorating the appearance, durability or weatherability of both highsolids and low solids coating compositions that are often used in OEMautomotive and truck manufacturing and to refinish or repaint automobileand truck bodies or parts thereof.

SUMMARY OF THE INVENTION

The present invention provides for a rheology control agent and the useof the agent in coating compositions to improve rheology control of bothlow and high solids solvent-borne and water-borne coating compositionsthat are useful in OEM painting or refinishing or repainting theexterior of automobile and truck bodies and parts thereof.

The rheology control agent of this invention comprises a compounddescribed by Formula (I) or (II) including isomers or mixtures ofisomers thereof:

wherein

-   -   p is 0, 1, 2, or 3;        wherein    -   R⁴ independently is a C4 to C16 linear or branched alkyl group;        a C5 to C12 cycloaliphatic group; a C6 to C16 cycloaliphatic        group bearing a linear or branched C1 to C8 alkyl group; a        (—CH₂CH₂—O)_(n)—CH₃ group with n being independently 1 to 8;        wherein    -   if p is 0, R² is a C3 to C16 linear or branched alkyl group, a        C1 to C6 linear or branched alkyl group bearing a C5-C16        cycloaliphatic group, a C5-C16 cycloaliphatic or alkyl        substituted cycloaliphatic group; and R³ is a C4 to C12 branched        alkylene group; a —(CH₂)_(w)OC(O)—(CH₂)_(s)C(O)O(CH₂)_(t)— group        with w and t equal to 1, 2, or 3 and s equal to 1 to 12; a        —CHR⁶C(O)O—R⁸—OC(O)CHR⁷— group with R⁸ equal to a C3 to C16        linear or branched alkylene group, a C1 to C6 linear or branched        alkylene group bearing a C5-C16 cycloaliphatic group, a C5-C16        cycloaliphatic or alkyl substituted cycloaliphatic group, a        (—CH₂CH₂—O—CH₂CH₂—)_(m) group with m being 1 to 4, and with R⁶        and R⁷ independently equal to a methyl, isopropyl, benzyl, or        isobutyl group and X is NH;        wherein    -   if p is 1, R² is a C1 to C8 linear or branched alkylene group, a        —(CH₂CH₂—O)_(n)—CH₂CH₂— group with n being 1 to 4,        wherein    -   if p is 2, R² is Formula (IIIa) and if p is 3, R² is Formula        (IIIb)

wherein

-   -   q is 0 or 1; and R⁵ is H, a C1 to C5 linear alkyl group;        wherein    -   if p is 1, 2, or 3, R³ is a C3 to C16 linear or branched        alkylene group, a C1 to C6 linear or branched alkylene group        bearing a C5-C16 cycloaliphatic group, a C5-C16 cycloaliphatic        or alkyl substituted cycloaliphatic group; R⁴ is as described        above;

wherein

-   -   if p is 1, 2, or 3, X and Y are chosen from O or NH with the        proviso that if X is O, Y cannot be O and if X is NH, Y cannot        be NH, Y may also be nothing, Z is chosen from O, NH, or        nothing; or    -   formula (II)

wherein

-   -   R is a C3 to C16 linear or branched alkylene group, a C1 to C6        linear or branched alkylene group bearing a C5-C16        cycloaliphatic group, a C5-C16 cycloaliphatic or alkyl        substituted cycloaliphatic group, R⁹ is a C1 to C8 linear or        branched alkylene group, a —(CH₂CH₂—O)_(n)—CH₂CH₂— group with n        being 1 to 4, and R¹⁰ is a C3 to C16 linear or branched,        alkylene group linkage;        wherein    -   n=1-7, m=1-7.

Solvent-borne and water-borne coating compositions containing the aboverheology control agents and a substrate having adhered thereto a layerof the coating a composition containing the above rheology control agentalso are part of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The features and advantages of the present invention will be morereadily understood, by those of ordinary skill in the art, from readingthe following detailed description. It is to be appreciated thosecertain features of the invention, which are, for clarity, describedabove and below in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures of the invention that are, for brevity, described in thecontext of a single embodiment, may also be provided separately or inany sub-combination. In addition, references in the singular may alsoinclude the plural (for example, “a” and “an” may refer to one, or oneor more) unless the context specifically states otherwise.

The use of numerical values in the various ranges specified in thisapplication, unless expressly indicated otherwise, are stated asapproximations as though the minimum and maximum values within thestated ranges were both proceeded by the word “about.” In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum values.

All patents, patent applications and publications referred to herein areincorporated by reference in their entirety.

The rheology control agents of this invention are typically used insolvent-borne coating compositions and in water-borne coatingcompositions, particularly clear and pigmented coating compositions usedfor OEM painting or for refinishing or repainting the exterior ofautomobiles and trucks and parts thereof. The rheology control agentimproves the rheology of the coating compositions to facilitate sprayapplications and provide a Class A automotive finish having an excellentoverall appearance, good DOI and flows out but does not sag or runparticularly when spray applied to vertical surfaces. Also, the rheologycontrol agents provide for the proper orientation of flake or specialeffects pigments when used in base coats or mono coats and improvesflake and pigment anti settling properties of coating compositions. Therheology control agents also can be used in primers, primer surfacersand primer fillers.

A compound which can provide rheology control to a coating compositionmust be compatible with the coating composition and not deteriorate theproperties of the resulting finish, such as, gloss and DOI or theweatherability or durability of the finish. Small changes in thechemical composition of a compound can significantly affect its use as arheology control agent. Rheological measurements are useful incharacterizing the effectiveness of a rheology control agent, but thefinal measure of the ability of a compound to provide effective rheologycontrol in a coating composition, is to test the compound in a coatingcomposition using conventional application conditions such as sprayapplication, optionally, with subsequent drying or baking of theresulting finish and observe the resulting appearance of the finish.

Typically, solvent-borne coating and water-borne coating compositionscomprise 5 to 95 percent by weight solvent or aqueous carrier, based onthe weight of the coating composition, and 5 to 95 percent by weight ofbinder, which includes the rheology control agent. Typically, the levelof rheology control agent in such compositions is in the range of 0.1 to30 percent by weight, based on the weight of the binder, and preferably,0.1 to 10 percent by weight based on the weight of the binder.

The rheology control agents also can be used in 100% binder solidscompositions in the ranges shown above.

The term “binder” as used herein refers to the film forming constituentsof the composition and includes any crosslinking components, such as,polyisocyanates, optional polymeric and/or oligomeric components, andoptional reactive diluents. Solvents, pigments, catalysts, antioxidants,U.V. absorbers, light stabilizers, leveling agents, antifoaming agents,anti-cratering agents, adhesion promoting agents are not included in theterm.

Molecular weight (both number and weight average) is determined by gelpermeation chromatography utilizing a high performance liquidchromatograph supplied by Hewlett-Packard, Palo Alto, Calif. and unlessotherwise stated the liquid phase used was tetrahydrofuran and thestandard was polymethylmethacrylate or polystyrene.

“Tg” (glass transition temperature) is in ° C. and determined byDifferential Scanning Calorimetry or calculated according to the FoxEquation.

“Lacquer” is a coating composition which dries via solvent, water or amixture of solvent and water evaporation without any substantialcrosslinking of the binder of the coating composition.

The rheology control agent of this invention useful in theaforementioned coating compositions as a rheology control agentcomprises at least one of the following compositions or mixtures thereofrepresented by the following formula:

wherein

-   -   p is 0, 1, 2, or 3;        wherein    -   R⁴ independently is a C4 to C16 linear or branched alkyl group;        a C5 to C12 cycloaliphatic group; a C6 to C16 cycloaliphatic        group bearing a linear or branched C1 to C8 alkyl group; a        (—CH₂CH₂—O)_(n)—CH₃ group with n being independently 1 to 8;        wherein    -   if p is 0, R² is a C3 to C16 linear or branched alkyl group, a        C1 to C6 linear or branched alkyl group bearing a C5-C16        cycloaliphatic group, a C5-C16 cycloaliphatic or alkyl        substituted cycloaliphatic group; R³ is a C4 to C12 branched        alkylene group; a —(CH₂)_(w)OC(O)—(CH₂)_(s)C(O)O(CH₂)_(t)— group        with w and t equal to 1, 2, or 3 and s equal to 1 to 12; a        —CHR⁶C(O)O—R⁸—OC(O)CHR⁷— group with R⁸ equal to a C3 to C16        linear or branched alkylene group, a C1 to C6 linear or branched        alkylene group bearing a C5-C16 cycloaliphatic group, a C5-C16        cycloaliphatic or alkyl substituted cycloaliphatic group, a        (—CH₂CH₂—O—CH₂CH₂—)_(m), group with m being 1 to 4, and with R⁶        and R⁷ independently equal to a methyl, isopropyl, benzyl, or        isobutyl group and X is NH;        wherein    -   if p is 1, R² is a C1 to C8 linear or branched alkylene group, a        (—CH₂CH₂—O)_(n)—CH₂CH₂— group with n being 1 to 4,        wherein    -   if p is 2, R² is Formula (IIIa) and if p is 3, R² is Formula        (IIIb)

wherein

-   -   q is 0 or 1; and R⁵ is H or a C1 to C5 linear alkyl group;        wherein    -   if p is 1, 2, 3, R³ is a C3 to C16 linear or branched alkylene        group, a C1 to C6 linear or branched alkylene group bearing a        C5-C16 cycloaliphatic group, a C5-C16 cycloaliphatic or alkyl        substituted cycloaliphatic group; and R⁴ is as defined above;        wherein    -   if p is 1, 2, 3 X and Y are chosen from O or NH with the proviso        that if X is O, Y cannot be O and if X is NH, Y cannot be NH, Y        may also be nothing, Z is chosen from O, NH, or nothing; or    -   formula (II)

-   -   wherein R is a C3 to C16 linear or branched alkylene group, a C1        to C6 linear or branched alkylene group bearing a C5-C16        cycloaliphatic group, a C5-C16 cycloaliphatic or alkyl        substituted cycloaliphatic group, R⁹ is a C1 to C8 linear or        branched alkylene group, a —(CH₂CH₂—O)_(n)—CH₂CH₂— group with n        being 1 to 4, and R¹⁰ is a C3 to C16 linear or branched,        alkylene group linkage;    -   wherein n=1-7, m=1-7.

The following formulas illustrate particularly useful rheology controlagents of this invention that provide solvent-borne coatings,water-borne coatings or 100% solids coatings with excellent rheologycontrol and form finishes that have excellent overall appearance, goodDOI, do not sag or run on application and good metal flake orientation.Further, these rheology control agents can be used in conjunction with awide variety of coating compositions containing as the binder,polyacrylates, polymethacrylates, branched, grafted or segmentedpoly(meth)acrylates, acrylic alkyd resins, polyesters, branchedpolyesters, oligomers, polyesterurethanes. These coating compositionsmay also utilize crosslinking agents, such as, polyisocyanates,alkylated melamines, melamine derivatives, and epoxides. These coatingcompositions may contain pigments and/or metal flakes.

Preferred rheology control agents in the first embodiment are forexample structures (IV) to (XVI). These structures are defined byformula (I) with p equal to 1, X equal to NH, Y equal to O and Z equalto NH, with R²-R⁴ as defined above.

The rheology control agents (IV) to (XVI) are prepared by first reactingan amino alcohol component with a diisocyanate component. The reactiontemperature, conditions and reactant concentration are selected to favorthe formation of the intermediate addition product, a bis-urea diolderivative. Further reaction with a mono-isocyanate component forms therheology control agent of this invention.

In another preferred embodiment, the present invention relates tocompounds with for example the structure of formula (XVII). Thesestructures are defined by formula (I) with p equal to 1, X equal to O, Yequal to NH and Z equal to NH, with R²-R⁴ as defined above.

These rheology control agents are prepared by first reacting a aminoalcohol component with a monoisocyanate component. The obtainedurea-alcohol is further reacted with a diisocyanate component.

In another preferred embodiment, the present invention relates tocompounds with for example the structure of formulae (XVIII) to (XXII).These structures are defined by formula (I) with p equal to 1, X equalto NH, Y equal to O and Z equal to nothing, with R²-R⁴ as defined above.

These rheology control agents are prepared by first reacting an aminoalcohol component with a diisocyanate component. The reactiontemperature and reactant concentration is selected to favor theselective formation of the intermediate addition product. Furtherreaction with an acylation equivalent (known to those skilled in theart, such as, acyl chlorides, carboxylic anhydrides) forms the rheologycontrol agent of this invention.

In another preferred embodiment, the present invention relates tocompounds with for example the structure of formulae (XXIII) and (XXIV).These structures are defined by formula (I) with p equal to 2, X equalto NH, Y equal to O and Z equal to NH, with R³-R⁴ as defined above, withR² equal to

with R⁵ equal to H and q equal to 0.

These rheology control agents are prepared by first reacting an aminobis-alcohol component with a diisocyanate component. The reactiontemperature, conditions and reactant concentration is selected to favorthe formation of the intermediate addition product, a bis-urea tetraolderivative. Further reaction with a mono-isocyanate component forms therheology control agent of this invention.

In another preferred embodiment, the present invention relates tocompounds with for example the structure of formulae (XXV). Thesestructures are defined by formula (I) with p equal to 3, X equal to NH,Y equal to O and Z equal to nothing, with R³-R⁴ as defined above, withR² equal to

These rheology control agents are prepared by first reacting an aminotris-alcohol component with a diisocyanate component. The reactiontemperature, conditions and reactant concentration is selected to favorthe formation of the intermediate addition product, a bis-urea hexanolderivative. Further reaction with an acylation equivalent (known tothose skilled in the art, such as acyl chlorides, carboxylic anhydrides)forms the rheology control agent of this invention.

In another preferred embodiment, the present invention relates tocompounds with for example the structure of formulae (XXVI) to (XXIX).These structures are defined by formula (I) with p equal to 0, X equalto NH, with R² is as defined above and R³ is a branched alkylene group.

These rheology control agents are prepared by reacting an diisocyanate,in the indicated examples 2-methyl-1,5-pentamethylene diisocyanate, withtwo equivalents of monoamine, alternatively these compounds may beprepared by reacting the corresponding diamine, such as2-methyl-1,5-pentamethylene diamine, with two equivalents of the alkylmonoisocyanate.

In another preferred embodiment, the present invention relates tocompounds with for example the structures of formula (XXX) to (XXXV).These structures are defined by formula (I) with p equal to 0, X equalto NH, with R² as defined above and R³ being a—(CH₂)_(w)OC(O)—(CH₂)_(s)C(O)O(CH₂)_(t)— group with w, t equal to 1, 2,or 3 and 5 equal to 1 to 12 (note when p is 0, R⁴ is also 0).

These rheology control agents are prepared by first reacting an aminoalcohol component with a monoisocyanate component. This intermediateurea alcohol is further reacted with a difunctional acylating componentequivalent (known to those skilled in the art, such as bis-acylchlorides, or bis-carboxylic anhydrides) to form the rheology controlagent. Alternatively, the parent bis-carboxylic acids may be utilized ina selective esterification reaction to form the desired products.

In another preferred embodiment, the present invention relates tocompounds with, for example, the structures of formula (XXXVI) to(XLII). These structures are defined by formula (I) with p equal to 1, Xequal to NH, Y equal to nothing, with Z equal to O, with R²-R⁴ asdefined above.

These rheology control agents are prepared by reacting two equivalentsof an alpha-amino ester component with a diisocyanate component.Alternatively, two equivalents of a glycin-ester derived isocyanate or alonger chain ester isocyanate can be used in a reaction with a diamineto form these structures.

In another preferred embodiment, the present invention relates tocompounds with for example the structure of formula (XLIII). Thisstructure is defined by formula (I) with p equal to 0, X equal to NH, R²is as defined above, R³ equal to a —CHR⁶C(O)O—R⁸—OC(O)CHR⁷— group, withR⁶, R⁷ and R⁸ defined as above. This rheology control agent is preparedby reacting a diol with an amino acid under esterification conditions,followed by isolation of the amino-acid di-ester. This di-ester isreacted with a two equivalents of monoisocyanate to form the product.

In another preferred embodiment, the present invention relates tocompounds with for example the structure of formula (XLIV). Thisstructure is defined by formula (II) with R⁹ and R¹⁰ defined as above.

wherein n=1-7, m=1-7.

In another preferred embodiment, the present invention relates tocompounds with, for example, the structure of formula (II) having thefollowing formulas:

Generally, compounds (IV) to (XLIV), (LII) and (LIII) may be formedusing a variety of routes for chemical synthesis. One such route forexample may be based on reacting an amine with an isocyanate in asuitable reaction vessel generally at a temperature between 0° C. and120° C., preferably, from 10° C. to 80° C., optionally, in the presenceof a diluent. Depending on the specific rheology control agent of thisinvention the synthesis might be formally separated into several steps.These steps may be carried out sequentially in one reaction vessel or indifferent reaction vessels followed by separation and/or purificationsteps. Certain rheology control agents of this invention may be formedby first reacting an amino alcohol component with a monoisocyanatecomponent. This intermediate is further reacted with a diisocyanatecomponent to form the rheology control agent. Certain rheology controlagents of this invention may be formed by first reacting an aminoalcohol component with a monoisocyanate component. This intermediate isfurther reacted with a difunctional acylating component equivalent(known to those skilled in the art, such as, acyl chlorides, carboxylicanhydrides) to form the rheology control agent. Certain rheology controlagents are formed by first reacting an amino alcohol component with adiisocyanate component. The reaction temperature and reactantconcentration is selected to favor the formation of the intermediateaddition product. Further reaction with a mono-isocyanate componentforms the rheology control agent of this invention. Certain rheologycontrol agents are formed by first reacting an amino alcohol componentwith a diisocyanate component. The reaction temperature and reactantconcentration is selected to favor the selective formation of theintermediate addition product. Further reaction with an acylationequivalent (known to those skilled in the art, such as, acyl chlorides,carboxylic anhydrides) forms the rheology control agent of thisinvention. Certain rheology control agents of this invention are formedby reaction of mono-isocyanates with diamines. Certain rheology controlagents of this invention are formed by reaction of mono-amine withdiisocyanates. Other rheology control agents of this invention areformed by first reacting an amino alcohol component with a diisocyanatecomponent. The reaction temperature and reactant concentration isselected to favor the formation of the intermediate addition product.This intermediate is further reacted with a lactone component to formthe rheology control agent.

The rheology control agent can be formulated, dissolved or dispersed intypical organic solvents or an aqueous carrier. More preferably, thesolvent is a ketone, ester, acetate, blend of ester and alcohol, aproticamide, aprotic sulfoxide, or aprotic amine. Examples of useful solventsinclude methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone,amyl acetate, ethylene glycol butyl ether acetate, propylene glycolmonomethyl ether acetate, xylene, N-methylpyrrolidone, blends of acetateand butanol or blends of aromatic hydrocarbons.

The rheology control agent of this invention can be combined with thefilm forming coating system using a range of methods. The rheologycontrol agent can be added to the film forming coating mixture as asolid in powder form. The use of agitation methods as known to thoseskilled in the art may be used to disperse, dissolve or distribute therheology control agent. The use of a high speed disperser has been foundto be a particularly effective dispersing technique at dispersing theserheology control agents in a binder component and solvent or aqueouscarrier of the coating formulation. This dispersion is subsequentlyadded to the other components of the coating formulation to make thefinal coating composition. Alternatively, the rheology control agent canbe prepared directly using the binder system of the film forming coatingmixture as the reaction medium using the general synthesis proceduresoutlined above.

Conventional rheology control agents has been produced in the presenceof a binder resin, as shown, for example, in GB 1454414, wherein a ureaadduct is prepared in situ in the presence of the binder. The rheologycontrol agents of this invention may also be produced in the presence ofa binder to form directly the desired rheologically active structure inthe binder resin. The extension of such structure formation can beadjusted as known to those skilled in the art using, for example, ashear treatment, or by modifying the mixing conditions.

The rheology control agents of this invention may also be preparedfollowing the outlined synthesis procedures directly from the startingmaterials described above by using a non-solvent, which has a limitedsolubility for the product. This strategy results in a precipitate thatcan be used as such, be milled in order to reduce the average length, orbe re-crystallized, for example, to increase the purity or to change thestructural morphology or fibril length. In the preparation process ofthe rheology control agent the dosing conditions or the stirrer speedcan be changed to influence the average structure build or fiberformation. Alternatively, the rheology control agent of this inventioncan be prepared as a true solution at temperatures between 0 and 150° C.If the solvent is selected such that it has affinity for the binder, thesolution can be combined with said binder and form the rheologycontrolling structure such as a fiber directly in said binder. Suitablesolvents for this purpose are, for example, N-methyl pyrrolidone (NMP)or dimethyl acetamide, n-butanol, or other aliphatic alcohols, oraliphatic diols, or butylglycol.

Alternatively, the rheology control agents of this invention may also beutilized in the form of their solutions in a polar aprotic solventcontaining 0.1-3.0 mols of an additive per urea group. The rheologycontrol agents of this invention as defined above have a solids contentof 10-75 wt. % and preferably of 15-40 wt. %. These solutions of therheology control agent can be used as additives for a coatingformulation.

Optionally, inorganic compounds can be added to maximize the solidscontent and stability of these solutions. By stability is meant nosignificant precipitation upon aging either at room temperature or atelevated temperature (up to 50° C.) storage. Preferred inorganiccompounds used in these solutions and are selected from LiCl, LiBr,NaCl, KCl, CaCl2, LiNO3, LiOC(O)Me or other Li-salts of carboxylicacids, benzoic acids or substituted benzoic acids, with LiCl as thepreferred inorganic compound. Surprisingly, it has been found that someof these rheology control agents can be dissolved at high solids (>10%by weight) in solvent without the use of these inorganic compounds.

The novel rheology control agents are useful in a wide variety ofsolvent-borne or water-borne coating compositions, such as, clearcoating compositions, base coating compositions, pigmented mono coatingcompositions, primer surfacers, primer fillers and sealers. Typicalbinders used in these compositions are acrylic polymers, such as,poly(meth)acrylates, meaning both polyacrylates and poly(meth)acrylates,branched, grafted or segmented poly(meth)acrylates, polyacrylourethanes,polyesters, branched copolyesters, oligomers, polyester urethanes andpolyepoxides. Typical crosslinking agents which may be used in thesecompositions are polyisocyanates, blocked polyisocyanates, melaminecrosslinking agents, alkylated melamines, silanes, benzoguanamines andother crosslinking agents known to those skilled in the art.

The acrylic polymers used to form the novel coating composition of thisinvention may be random polymers or structured copolymers, such as,block or graft copolymers. Particularly useful structured polymers arebranched acrylic polymers having segmented arms as disclosed in U.S.Ser. No. 10/983,462 filed on Nov. 8, 2004 and U.S. Ser. No. 10/983,875filed on Nov. 8, 2004, both of which are incorporated herein byreference.

A block copolymer used in the present invention may have an AB diblockstructure, or ABA or ABC triblock structure, for example. Graftcopolymers can be used in the present invention having a backbonesegment and a side chain segment(s). Random copolymers that can be usedhave polymer segments randomly distributed in the polymer chain.

Acrylic AB, ABA or ABC block copolymers can be prepared by using astepwise polymerization process such as anionic, group transferpolymerization (GTP) taught in U.S. Pat. No. 4,508,880, Webster et al.,““Living” polymers and process for their preparation”, atom transferradical polymerization (ATRP) taught in U.S. Pat. No. 6,462,125, Whiteet al., and radical addition fragmentation transfer (RAFT) taught inU.S. Pat. No. 6,271,340, Anderson, et al. “Method of controlling polymermolecular weight and structure”. All of the above, herein incorporatedby reference. Polymers so produced have precisely controlled molecularweight, block sizes and very narrow molecular weight distributions.

Aqueous coating compositions containing AB block copolymers as pigmentdispersants disclosed in Houze et al. U.S. Pat. No. 6,204,319, which ishereby incorporated by reference, can utilize the novel rheology controlagents of this invention.

Graft copolymers may be prepared by a macromonomer approach using thespecial cobalt chain transfer (SCT) method reported in U.S. Pat. No.6,472,463, Ma, the disclosure of which is herein incorporated byreference.

Random copolymers can be prepared using conventional free radicalpolymerization techniques as described in U.S. Pat. No. 6,451,950, Ma,the disclosure of which is herein incorporated by reference.

Typically useful acrylic polymers have a number average molecular weightof about 1,000 to 100,000, a Tg of 10 to 100° C. and contain moieties,such as, hydroxyl, carboxyl, glycidyl and amino groups. Typically usefulacrylic polymers are known in the art and the following are typicalexamples of monomers used to form such polymers: linear alkyl(meth)acrylates having 1 to 12 carbon atoms in the alkyl group, cyclicor branched alkyl(meth)acrylates having 3 to 12 carbon atoms in thealkyl group including isobornyl(meth)acrylate, hydroxyalkyl(meth)acrylates having 1 to 4 carbon atoms in the alkyl group,glycidyl(meth)acrylate, hydroxy amino alkyl(meth)acrylates having 1 to 4carbon atoms in the alkyl group, and the polymers can contain styrene,alpha methyl styrene, vinyl toluene, (meth)acrylonitrile(meth)acrylamides, (meth)acrylic acid, (meaning both acrylic acid and methacrylicacid) trimethoxysilylpropyl (meth)acrylate and the like.

Examples of (meth)acrylic acid esters useful for forming these acrylicpolymers are methyl acrylate, ethyl acrylate, isopropyl acrylate,tert.-butyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexylacrylate, lauryl acrylate, stearyl acrylate and the correspondingmethacrylates. Examples of (meth)acrylic acid esters with cyclicalcohols are cyclohexyl acrylate, trimethylcyclohexyl acrylate,4-tert.-butylcyclohexyl acrylate, isobornyl acrylate and thecorresponding methacrylates.

Additional unsaturated monomers that do not contain additionalfunctional groups useful for forming the acrylic polymers are, forexample, vinyl ethers, such as, isobutyl vinyl ether and vinyl esters,such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons,preferably those with 8 to 9 carbon atoms per molecule. Examples of suchmonomers are styrene, alpha-methylstyrene, chlorostyrenes,2,5-dimethylstyrene, p-methoxystyrene, vinyl toluene. Styrene ispreferably used.

Small proportions of olefinically polyunsaturated monomers may also beused. These are monomers having at least 2 free-radically polymerizabledouble bonds per molecule. Examples of these are divinylbenzene,1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycoldimethacrylate, glycerol dimethacrylate.

Hydroxy-functional (meth)acrylic polymers generally are formed byfree-radical copolymerization using conventional processes well known tothose skilled in the art, for example, bulk, solution or beadpolymerization, in particular by free-radical solution polymerizationusing free-radical initiators.

Suitable hydroxyl-functional unsaturated monomers that are used tointroduce hydroxyl groups into the acrylic polymer are, for example,hydroxyalkyl esters of alpha, beta-olefinically unsaturatedmonocarboxylic acids with primary or secondary hydroxyl groups. Thesemay, for example, comprise the hydroxyalkyl esters of acrylic acid,methacrylic acid, crotonic acid and/or isocrotonic acid. Thehydroxyalkyl esters of (meth)acrylic acid are preferred. Examples ofsuitable hydroxyalkyl esters of alpha, beta-olefinically unsaturatedmonocarboxylic acids with primary hydroxyl groups arehydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate,hydroxybutyl(meth)acrylate, hydroxyamyl(meth)acrylate,hydroxyhexyl(meth)acrylate. Examples of suitable hydroxyalkyl esterswith secondary hydroxyl groups are 2-hydroxypropyl(meth)acrylate,2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate.

Preferred are hydroxy functional acrylic polymers having a hydroxyequivalent weight of 300 to 1300 and are polymers of hydroxyalkyl(meth)acrylates and one or more of the aforementioned monomers. Thehydroxyl equivalent weight is the grams of resin per equivalent ofhydroxyl groups. The following are typically preferred acrylic polymers:styrene/methyl methacrylate/isobutylmethacrylate/hydroxyethyl(meth)acrylate; styrene/methylmethacrylate/isobutyl methacrylate/2-ethylhexyl methacrylate/isobornylmethacrylate/hydroxyethyl(meth)acrylate and styrene/isobornylmethacrylate/2-ethylhexyl methacrylate/hydroxy propylmethacrylate/hydroxyethyl(meth)acrylate. One particularly preferredhydroxy containing acrylic polymer contains 35 to 50% by weight styrene,15 to 25% by weight ethylhexyl methacrylate and 15 to 20% by weightisobornyl methacrylate and 20 to 30% by weight hydroxyethylmethacrylate.

Additional useful hydroxy-functional unsaturated monomers are reactionproducts of alpha, beta-unsaturated monocarboxylic acids with glycidylesters of saturated monocarboxylic acids branched in alpha position, forexample with glycidyl esters of saturatedalpha-alkylalkanemonocarboxylic acids oralpha,alpha′-dialkylalkanemonocarboxylic acids. These preferablycomprise the reaction products of (meth)acrylic acid with glycidylesters of saturated alpha,alpha-dialkylalkanemonocarboxylic acids with 7to 13 carbon atoms per molecule, particularly preferably with 9 to 11carbon atoms per molecule. These reaction products may be formed before,during or after the copolymerization reaction.

Further usable hydroxy-functional unsaturated monomers are reactionproducts of hydroxyalkyl(meth)acrylates with lactones.Hydroxyalkyl(meth)acrylates which may be used are, for example, thosestated above. Suitable lactones are, for example, those that have 3 to15 carbon atoms in the ring, wherein the rings may also comprisedifferent substituents. Preferred lactones are gamma-butyrolactone,delta-valerolactone, epsilon-caprolactone,beta-hydroxy-beta-methyl-delta-valerolactone, lambda-laurolactone ormixtures thereof. Epsilon-caprolactone is particularly preferred. Thereaction products preferably comprise those prepared from 1 mole of ahydroxyalkyl ester of an alpha, beta-unsaturated monocarboxylic acid and1 to 5 moles, preferably on average 2 moles, of a lactone. The hydroxylgroups of the hydroxyalkyl esters may be modified with the lactonebefore, during or after the copolymerization reaction.

Suitable unsaturated monomers that can be used to provide the acrylicpolymer with carboxyl groups are, for example, olefinically unsaturatedmonocarboxylic acids, such as, for example, acrylic acid, methacrylicacid, crotonic acid, isocrotonic acid, itaconic acid. Acrylic acid andmethacrylic acid are preferably used.

Suitable unsaturated monomers that can be used to provide the acrylicpolymer with glycidyl groups are, for example, allyl glycidyl ether,3,4-epoxy-1-vinylcyclohexane, epoxycyclohexyl(meth)acrylate, vinylglycidyl ether and glycidyl(meth)acrylate. Glycidyl(meth)acrylate ispreferably used.

Free-radically polymerizable, olefinically unsaturated monomers which,apart from at least one olefinic double bond, do not contain additionalfunctional groups that can be used to form the acrylic polymer are, forexample, esters of unsaturated carboxylic acids with aliphaticmonohydric branched or unranked as well as cyclic alcohols with 1 to 20carbon atoms. The unsaturated carboxylic acids, which may be considered,are acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid.Esters of (meth)acrylic acid are preferred.

The acrylic polymer can contain (meth)acrylamides. Typical examples ofsuch acrylic polymers are polymers of (meth)acrylamide andalkyl(meth)acrylates, hydroxy alkyl(meth)acrylates, (meth)acrylic acidand or one of the aforementioned ethylenically unsaturated polymerizablemonomers.

Acrylic oligomers having a number average molecular weight of 300 to3,000 of the aforementioned monomeric components also can be used as anoptional polymeric component. Useful acrylic oligomers are disclosed inU.S. Ser. No. 10/617,585 filed Jul. 11, 2003. By using monomers andreactants well known to those skilled in the art, these oligomers canhave the one or more of the following groups that are reactive withisocyanate: hydroxyl, carboxyl, glycidyl, amine, aldimine, phosphoricacid and ketimine.

Acrylourethanes also can be used to form the novel coating compositionof this invention. Typical useful acrylourethanes are formed by reactingthe aforementioned acrylic polymers with an organic polyisocyanate.Generally, an excess of the acrylic polymer is used so that theresulting acrylourethane has terminal acrylic segments having reactivegroups as described above. These acrylourethanes can have reactive endgroups and/or pendant groups such as hydroxyl, carboxyl, amine,glycidyl, amide, silane or mixtures of such groups. Useful organicpolyisocyanates are described hereinafter as the crosslinking componentbut also can be used to form acrylourethanes useful in this invention.Typically useful acrylourethanes are disclosed in Stamegna et al. U.S.Pat. No. 4,659,780, which is hereby incorporated by reference.

Polyesters can also be used, such as, hydroxyl or carboxyl terminated orhydroxyl or carboxyl containing polyesters. The following are typicallyuseful polyesters or ester oligomers: polyesters or oligomers ofcaprolactone diol and cyclohexane dimethylol, polyesters or oligomers oftris-hydroxy ethylisocyanurate and caprolactone, polyesters or oligomersof trimethylol propane, phthalic acid or anhydride and ethylene oxide,polyesters or oligomers of pentaerythritol, hexahydrophthalic anhydrideand ethylene oxide, polyesters or oligomers of pentaerythritol,hexahydrophthalic anhydride and butylene oxide as disclosed in U.S. Pat.No. 6,221,484 B1.

The aforementioned polyesters and oligomers can be reacted with anorganic isocyanate to form polyesterurethane polymers and oligomers thatcan be used in the novel composition.

One useful polyesterurethane that can used in the composition is formedby reacting an aliphatic polyisocyanate with an aliphatic orcycloaliphatic monohydric alcohol and subsequently reacting theresulting composition with a hydroxy functional aliphatic carboxylicacid until all of the isocyanate groups have been reacted. One usefulpolyurethane oligomer comprises the reaction product of the isocyanurateof hexane diisocyanate, cyclohexanol and dimethylol propionic acid.

Useful branched copolyesters polyols and the preparation thereof aredescribed in WO 03/070843 published Aug. 28, 2003, which is herebyincorporated by reference.

The branched copolyester polyol has a number average molecular weightnot exceeding 30,000, alternately in the range of from 1,000 to 30,000,further alternately in the range of 2,000 to 20,000, and still furtheralternately in the range of 5,000 to 15,000. The copolyester polyol hashydroxyl groups ranging from 5 to 200 per polymer chain, preferably 6 to70, and more preferably 10 to 50, and carboxyl groups ranging from 0 to40 per chain, preferably 1 to 40, more preferably 1 to 20 and mostpreferably 1 to 10. The Tg (glass transition temperature) of thecopolyester polyol ranges from −70° C. to 50° C., preferably from −65°C. to 40° C., and more preferably from −60° C. to 30° C.

The branched copolyester polyol is conventionally polymerized from amonomer mixture containing a chain extender selected from the groupconsisting of a hydroxy carboxylic acid, a lactone of a hydroxycarboxylic acid and a combination thereof; and one or more hyperbranching monomers.

The following additional ingredients can be included in the coatingcomposition, particularly when the coating composition is useful as alacquer, in amounts of 0.1% to 98% by weight and alternately in therange of 50% to 95% by weight, all based on the weight of the binder ofthe coating composition:

Useful acrylic alkyd polymers having a weight average molecular weightranging from 3,000 to 100,000 and a Tg ranging from 0° C. to 100° C. areconventionally polymerized from a monomer mixture that can include oneor more of the following monomers: an alkyl(meth)acrylate, for example,methyl(meth)acrylate, butyl(meth)acrylate, ethyl(meth)acrylate, 2-ethylhexyl(meth)acrylate; a hydroxy alkyl(meth)acrylate, for example, hydroxyethyl(meth)acrylate, hydroxy propyl(meth)acrylate, hydroxybutyl(meth)acrylate; (meth)acrylic acid; styrene; and alkyl aminoalkyl(meth)acrylate, for example, diethylamino ethyl(meth)acrylate ort-butyl aminoethyl methacrylate; and one or more of the following dryingoils: vinyl oxazoline drying oil esters of linseed oil fatty acids, talloil fatty acids or tung oil fatty acids.

One preferred polymer is polymerized from a monomer mixture thatcontains an alkyl(meth)acrylate, hydroxy alkyl acrylate, alkylaminoalkyl acrylate and vinyl oxazoline ester of drying oil fatty acids.

Suitable iminiated acrylic polymers can be obtained by reacting acrylicpolymers having carboxyl groups with an alkylene imine, such aspropylene imine.

Suitable cellulose acetate butyrates are supplied by Eastman ChemicalCo., Kingsport, Tenn. under the trade names CAB-381-20 and CAB-531-1 andare preferably used in an amount of 0.1 to 20% by weight based on theweight of the binder.

A suitable ethylene-vinyl acetate co-polymer (wax) is supplied byHoneywell Specialty Chemicals—Wax and Additives, Morristown, N.J., underthe trade name A-C® 405 (T) Ethylene—Vinyl Acetate Copolymer.

Suitable nitrocellulose resins preferably have a viscosity of about ½-6seconds. Preferably, a blend of nitrocellulose resins is used.Optionally, the lacquer can contain ester gum and castor oil.

Suitable alkyd resins are the esterification products of a drying oilfatty acid, such as linseed oil and tall oil fatty acid, dehydratedcastor oil, a polyhydric alcohol, a dicarboxylic acid and an aromaticmonocarboxylic acid. Typical polyhydric alcohols that can be used toprepare the alkyd resin used in this invention are glycerine,pentaerythritol, trimethylol ethane, trimethylol propane; glycols, suchas, ethylene glycol, propylene glycol, butane diol and pentane diol.Typical dicarboxylic acids or anhydrides that can be used to prepare thealkyd resin are phthalic acid, phthalic anhydride, isophthalic acid,terephthalic acid maleic, and fumaric acid. Typical monocarboxylicaromatic acids are benzoic acid, paratertiary butylbenzoic acid, phenolacetic acid and triethyl benzoic acid. One preferred alkyd resin is areaction product of an acrylic polymer and an alkyd resin.

Suitable plasticizers include butyl benzyl phthalate, dibutyl phthalate,triphenyl phosphate, 2-ethylhexylbenzyl phthalate, dicyclohexylphthalate, diallyl toluene phthalate, dibenzyl phthalate,butylcyclohexyl phthalate, mixed benzoic acid and fatty oil acid estersof pentaerythritol, poly(propylene adipate) dibenzoate, diethyleneglycol dibenzoate, tetrabutylthiodisuccinate, butyl phthalyl butylglycolate, acetyltributyl citrate, dibenzyl sebacate, tricresylphosphate, toluene ethyl sulfonamide, the di-2-ethyl hexyl ester ofhexamethylene diphthalate, and di(methyl cyclohexyl)phthalate. Onepreferred plasticizer of this group is butyl benzyl phthalate.

If desired, the coating composition can include metallic driers,chelating agents, or a combination thereof. Suitable organometallicdriers include cobalt naphthenate, copper naphthenate, lead tallate,calcium naphthenate, iron naphthenate, lithium naphthenate, leadnaphthenate, nickel octoate, zirconium octoate, cobalt octoate, ironoctoate, zinc octoate, and alkyl tin dilaurates, such as dibutyl tindilaurate. Suitable chelating agents include aluminum monoisopropoxidemonoversatate, aluminum (monoisopropyl)phthalate, aluminumdiethoxyethoxide monoversatate, aluminum trisecondary butoxide, aluminumdiisopropoxide monoacetacetic ester chelate and aluminum isopropoxide.

Also, polytrimethylene ether diols may be used as an additive having anumber average molecular weight (Mn) in the range of from 500 to 5,000,alternately in the range of from 1,000 to 3,000; a polydispersity in therange of from 1.1 to 2.1 and a hydroxyl number in the range of from 20to 200. The preferred polytrimethylene ether diol has a Tg of −75° C.Copolymers of polytrimethylene ether diols are also suitable. Forexample, such copolymers are prepared by copolymerizing 1,3-propanediolwith another diol, such as, ethane diol, hexane diol,2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trimethylolpropane and pentaerythritol, wherein at least 50% of the copolymerresults from 1,3-propanediol. A blend of a high and low molecular weightpolytrimethylene ether diol can be used wherein the high molecularweight diol has an Mn ranging from 1,000 to 4,000 and the low molecularweight diol has an Mn ranging from 150 to 500. The average Mn of thediol should be in the range of 1,000 to 4,000. It should be noted that,the polytrimethylene ether diols suitable for use in the presentinvention can include polytrimethylene ether triols and other higherfunctionality polytrimethylene ether polyols in an amount ranging from 1to 20%, by weight, based on the weight of the polytrimethylene etherdiol. It is believed that the presence of polytrimethylene ether diolsin the crosslinked coating composition of this invention can improve thechip resistance of a coating resulting therefrom.

Additional details of the foregoing additives are provided in U.S. Pat.Nos. 3,585,160, 4,242,243, 4,692,481, and U.S. Pat. No. Re 31,309, whichare incorporated therein by reference.

Crosslinking Agents

Lacquer coating compositions can be formulated without the use of acrosslinking agent. Typical crosslinkable compositions that utilize thenovel rheology control agents are solvent borne compositions having abinder containing in the range of 25-95 percent by weight of one of theaforementioned film forming polymers and 5-75 percent by weight of acrosslinking agent. Preferably, the binder contains in the range of40-90 percent by weight of the film forming polymer and 10-60 percent byweight of the crosslinking agent. Useful crosslinking agents includeorganic polyisocyanates, blocked organic polyisocyanates, melamines,alkylated melamines, benzoquanamines, epoxides and silanes

Typically useful organic polyisocyanates crosslinking agents that can beused in the novel composition of this invention include aliphaticpolyisocyanates, cycloaliphatic polyisocyanates and isocyanate adducts.Typical polyisocyanates can contain within the range of 2 to 10,preferably 2.5 to 8, more preferably 3 to 5 isocyanate functionalities.Generally, the ratio of equivalents of isocyanate functionalities on thepolyisocyanate per equivalent of all of the functional groups presentranges from 0.5/1 to 3.0/1, preferably from 0.7/1 to 1.8/1, morepreferably from 0.8/1 to 1.3/1.

Examples of suitable aliphatic and cycloaliphatic polyisocyanates thatcan be used include the following: 4,4′dicyclohexyl methanediisocyanate, (“H₁₂MDI”), trans-cyclohexane-1,4-diisocyanate,1,6-hexamethylene diisocyanate (“HDI”), isophorone diisocyanate,(“IPDI”), other aliphatic or cycloaliphatic di-, tri- ortetra-isocyanates, such as, 1,2-propylene diisocyanate, tetramethylenediisocyanate, 2,3-butylene diisocyanate, octamethylene diisocyanate,2,2,4-trimethyl hexamethylene diisocyanate, dodecamethylenediisocyanate, omega-dipropyl ether diisocyanate, 1,3-cyclopentanediisocyanate, 1,2 cyclohexane diisocyanate, 1,4 cyclohexanediisocyanate, 4-methyl-1,3-diisocyanatocyclohexane,dicyclohexylmethane-4,4′-diisocyanate, 3,3′-dimethyl-dicyclohexylmethane4,4′-diisocyanate, polyisocyanates having isocyanurate structural units,such as, the isocyanurate of hexamethylene diisocyanate and theisocyanurate of isophorone diisocyanate, the adduct of 2 molecules of adiisocyanate, such as, hexamethylene diisocyanate, uretidiones ofhexamethylene diisocyanate, uretidiones of isophorone diisocyanate and adiol, such as, ethylene glycol, the adduct of 3 molecules ofhexamethylene diisocyanate and 1 molecule of water, allophanates,trimers and biurets of hexamethylene diisocyanate, allophanates, trimersand biurets of isophorone diisocyanate and the isocyanurate of hexanediisocyanate.

Tri-functional isocyanates also can be used, such as, Desmodur® N 3300,trimer of hexamethylene diisocyanate, Desmodur® 3400, trimer ofisophorone diisocyanate, Desmodur® 4470 trimer of isophoronediisocyanate, these trimers are sold by Bayer Corporation. A trimer ofhexamethylene diisocyanate sold as Tolonate® HDT from Rhodia Corporationis also suitable.

An isocyanate functional adduct can be used, such as, an adduct of analiphatic polyisocyanate and a polyol. Also, any of the aforementionedpolyisocyanates can be used with a polyol to form an adduct. Polyols,such as, trimethylol alkanes, particularly, trimethylol propane orethane can be used to form an adduct.

The melamine crosslinking agents are generally partially alkylatedmelamine formaldehyde compounds and may be monomeric or polymeric ormixtures thereof. Some of the suitable monomeric melamines include lowmolecular weight melamines which contain, on an average, three or moremethylol groups etherized with a C₁ to C₅ monohydric alcohol, such as,methanol, n-butanol, or isobutanol per triazine nucleus, and have anaverage degree of condensation up to about 2 and preferably in the rangeof about 1.1 to about 1.8, and have a proportion of mononuclear speciesnot less than about 50 percent by weight. By contrast the polymericmelamines have an average degree of condensation of more than 1.9.

Some such suitable monomeric melamines include alkylated melamines, suchas methylated, butylated, isobutylated melamines and mixtures thereof.Many of these suitable monomeric melamines are supplied commercially.For example, Cytec Industries Inc., West Patterson, N.J. supplies Cymel®301 (degree of polymerization of 1.5, 95% methyl and 5% methylol),Cymel® 350 (degree of polymerization of 1.6, 84% methyl and 16%methylol), 303, 325, 327 and 370, which are all monomeric melamines.Suitable polymeric melamines include high amino (partially alkylated)melamine known as Resimene® BMP5503 (molecular weight 690,polydispersity of 1.98, 56% butyl, 44% amino), which is supplied bySolutia Inc., St. Louis, Mo., or Cymel®1158 provided by Cytec IndustriesInc., West Patterson, N.J. Cytec Industries Inc. also supplies Cymel®1130 @ 80 percent solids (degree of polymerization of 2.5), Cymel® 1133(48% methyl, 4% methylol and 48% butyl), both of which are polymericmelamines.

If desired, appropriate catalysts may also be included in the activatedcompositions to accelerate the curing process of a potmix of the coatingcomposition.

When the activated compositions include melamine as the crosslinkingagent, it also preferably includes a catalytically active amount of oneor more acid catalysts to further enhance the crosslinking of thecomponents on curing. Generally, catalytically active amount of the acidcatalyst in the coating composition ranges from about 0.1 percent toabout 5 percent, preferably ranges from 0.1 percent to 2 percent, morepreferably ranges from 0.5 percent to 1.2 percent, all in weight percentbased on the weight of the binder. Some suitable acid catalysts includearomatic sulfonic acids, such as, dodecylbenzene sulfonic acid,para-toluenesulfonic acid and dinonylnaphthalene sulfonic acid, all ofwhich are either unblocked or blocked with an amine, such as, dimethyloxazolidine and 2-amino-2-methyl-1-propanol, n,n-dimethylethanolamine ora combination thereof. Other acid catalysts that can be used, such as,phosphoric acids, more particularly, phenyl acid phosphate, benzoicacid, oligomers having pendant acid groups, all of which may beunblocked or blocked with an amine.

When the activated compositions include a polyisocyanate as thecrosslinking agent, the coating composition preferably includes acatalytically active amount of one or more tin or tertiary aminecatalysts for accelerating the curing process. Generally, catalyticallyactive amount of the catalyst in the coating composition ranges fromabout 0.001 percent to about 5 percent, preferably ranges from 0.005percent to 2 percent, more preferably ranges from 0.01 percent to 1percent, all in weight percent based on the weight of the binder. A widevariety of catalysts can be used, such as, tin compounds, includingdibutyl tin dilaurate and dibutyl tin diacetate; tertiary amines, suchas, triethylenediamine. These catalysts can be used alone or inconjunction with carboxylic acids, such as, acetic acid. One of thecommercially available catalysts, sold under the trademark, Fastcat®4202 dibutyl tin dilaurate by Elf-Atochem North America, Inc.Philadelphia, Pa., is particularly suitable.

Carrier Medium

The liquid carrier medium comprises an organic solvent or blend ofsolvents or an aqueous carrier comprising water and optionally,compatible organic solvents. The coating compositions contain about 5-95percent, more typically 10-85 percent by weight of binder and about 5-95percent, more typically 15-90 percent by weight, of the liquid carrier(based on the weight of the coating composition). The selection oforganic solvent depends upon the requirements of the specific end useapplication of the coating composition of this invention, such as theVOC (volatile organic content) emission requirements, the selectedpigments, binder and crosslinking agents. Representative examples oforganic solvents which are useful herein include alcohols, such as,methanol, ethanol, n-propanol, and isopropanol; ketones, such as,acetone, butanone, pentanone, hexanone, and methyl ethyl ketone, methylisobutyl ketone, diisobutyl ketone, methyl amyl ketone; alkyl esters ofacetic, propionic, and butyric acids, such as ethyl acetate, butylacetate, and amyl acetate; ethers, such as tetrahydrofuran, diethylether, and ethylene glycol and polyethylene glycol monoalkyl and dialkylethers, such as, cellosolves and carbitols; and glycols, such as,ethylene glycol and propylene glycol and mixtures thereof, and aromatichydrocarbon solvents, such as, xylene, toluene. Typically, aqueouscarriers comprise water and a blend of organic solvents suited for therequirements of the coating composition.

Pigments

The coating composition containing the rheology control agent of thisinvention may be used as a base coat or as a pigmented mono-coattopcoat. Both of these compositions require the presence of pigments.Typically, a pigment-to-binder ratio of 0.1/100 to 200/100 is useddepending on the color and type of pigment used. The pigments areformulated into mill bases by conventional procedures, such as,grinding, sand milling, ball milling, high speed mixing, attritorgrinding and two or three roll milling. Generally, the mill basecomprises pigment and a dispersant in a liquid carrier. The mill base isadded in an appropriate amount to the coating composition with mixing toform a pigmented coating composition.

Any of the conventionally-used organic and inorganic pigments, such as,white pigments, like, titanium dioxide, color pigments, metallic flakes,such as, aluminum flake, special effects pigments, such as, coated micaflakes, coated aluminum flakes and the like, azo, anthraquinone,thioindigo, oxazine, quinacridone, lakes and toners of acidic dyestuffs, copper phthalocyanine and its derivatives, and various mixturesand modifications thereof and extender pigments can be used.

The coating composition containing the novel rheology control agent maybe used as a primer, primer surfacer or sealer in which case typicalpigments used in primers would be added, such as, carbon black, barytes,silica, iron oxide and other pigments that are commonly used in primersin a pigment-to-binder ratio of 10/100 to 300/100.

Coating Compositions and Additives to Improve Weatherability

The coating composition containing the novel rheology control agent ofthis invention can be used as a clear coat that is applied over apigmented base coat that may a pigmented version of the composition ofthis invention or another type of a pigmented base coat. The clearcoating can be in solution or in dispersion form.

Typically, a clear coating is applied over the base coating before thebase coating is fully cured. This is a so called “wet-on-wet process”.In this process, a base coating is applied to a substrate and flashdried and then the clear coating is applied and both layers are thenfully cured either at ambient temperatures or cured by heating toelevated temperatures, for example, of 50° C. to 100° C. for 15 to 45minutes to form a clear coat/base coat finish. When used in combinationwith a primer or primer-surfacer, the primer or primer-surfacer is alsoflash dried and then the base coating and clear coating are applied asabove. This is a so-called “wet on wet on wet” process. The base coatingand clear coating preferably have a dry coating thickness ranging from25 to 75 microns and 25 to 100 microns, respectively.

When refinishing automobile and truck bodies, the original OEM topcoatis usually sanded and a primer or sealer coat applied and then a monocoat or a basecoat/clear coat is applied. These coatings are usuallycured at ambient temperatures or at slightly elevated temperatures, suchas, 40 to 100° C.

To improve the weathering properties of clear coatings, the coatingcomposition contains about 0.1 to 5% by weight, based on the weight ofthe binder, of ultraviolet light absorbers. Typically useful ultravioletlight absorbers include hydroxyphenyl benzotriazols, such as,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert.amyl-phenyl)-2H-benzotriazole,2[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, reactionproduct of 2-(2-hydroxy-3-tert.butyl-5-methylpropionate)-2H-benzotriazole and polyethylene ether glycol having aweight average molecular weight of 300,2-(2-hydroxy-3-tert.butyl-5-iso-octyl propionate)-2H-benzotriazole;hydroxyphenyl s-triazines, such as,2-[4((2-hydroxy-3-dodecyloxy/tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4(2-hydroxy-3-(2-ethylhexyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-(4-octyloxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;hydroxybenzophenone U.V. absorbers, such as, 2,4-dihydroxybenzophenone,2-hydroxy-4-octyloxybenzophenone, and2-hydroxy-4-dodecyloxybenzophenone.

Clear coating compositions of the novel coating composition also maycontain about 0.1 to 5% by weight, based on the weight of the binder, ofa di-substituted phenol antioxidant or a hydroperoxide decomposer.Typically useful antioxidants includetetrakis[methylene(3,5-di-tert-butylhydroxy hydrocinnamate)]methane,octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,tris(2,4-di-tert-butylphenyl) phosphite,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trioneand benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9branched alkyl esters. Typically useful hydroperoxide decomposersinclude Sanko® HCA (9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide),triphenyl phosphate and other organo-phosphorous compounds, such as,Irgafos® TNPP from Ciba Specialty Chemicals, Irgafos® 168, from CibaSpecialty Chemicals, Ultranox® 626 from GE Specialty Chemicals, MarkPEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, Irgafos® P-EPQ fromCiba Specialty Chemicals, Ethanox 398 from Albemarle, Weston 618 from GESpecialty Chemicals, Irgafos® 12 from Ciba Specialty Chemicals, Irgafos®38 from Ciba Specialty Chemicals, Ultranox® 641 from GE SpecialtyChemicals and Doverphos® S-9228 from Dover Chemicals.

Clear coating compositions containing the novel rheology control agentalso may contain about 0.1-5% by weight, based on the weight of thebinder, of hindered amine light stabilizers. Typically useful hinderedamine light stabilizers includeN-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-dodecyl succinimide,N(1acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide,N-(2hydroxyethyl)-2,6,6,6-tetramethylpiperidine-4-ol-succinic acidcopolymer, 1,3,5 triazine-2,4,6-triamine,N,N′″-[1,2-ethanediybis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]bis[N,N′″-dibutyl-N′,N′″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)],poly-[[6-[1,1,3,3-tetramethylbutyl)-amino]-1,3,5-triazine-2,4-diyl][2,2,6,6-tetramethylpiperidinyl)-imino]-1,6-hexane-diyl[(2,2,6,6-tetramethyl-4-piperidinyl)-imino]),bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[3,5bis(1,1-dimethylethyl-4-hydroxy-phenyl)methyl]butylpropanedioate,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dion,dodecyl/tetradecyl-3-(2,2,4,4-tetramethyl-2l-oxo-7-oxa-3,20-diazaldispiro(5.1.11.2)henicosan-20-yl)propionate.

Other Additives

In addition, the coating composition containing the novel rheologycontrol agent may also contain a variety of other optional compatibleingredients, including fillers, plasticizers, antioxidants, surfactantsand flow control agents.

For example, such coating compositions may contain 0.1 to 30% by weight,based on the weight of the binder, of acrylic NAD (non-aqueousdispersed) resins. These NAD resins typically are high molecular weightresins having a crosslinked acrylic core with a Tg between 20 to 100° C.and attached to the core are low Tg stabilizer segments. A descriptionof such NADs is found in Antonelli et al. U.S. Pat. No. 4,591,533 and inBarsotti et al. U.S. Pat. No. 5,763,528 which patents are herebyincorporated by reference.

Also, such coating compositions may include other conventionalformulation additives known to those skilled in the art, such as,wetting agents, leveling and flow control agents, for example,Resiflow®S (polybutylacrylate), BYK® 320 and 325 (high molecular weightpolyacrylates), BYK® 347 (polyether-modified siloxane), rheology controlagents, such as, fumed silica, defoamers, surfactants and emulsifiers tohelp stabilize the composition. Other additives that tend to improve marresistance can be added, such as, silsesquioxanes and othersilicate-based micro-particles.

One particularly useful additive is a blend of the novel rheologycontrol agent and finely divided silica in a weight ratio of 0.1:1 to1:0.1. Other particularly useful additive is a blend of the novelrheology control agent and bis-urea crystals as mentioned in U.S. Pat.No. 4,311,622 in a weight ratio of 0.1:1 to 1:0.1.

The rheology control agent may be incorporated into one of thecomponents of a typical two component (2K) coating composition. Forexample, in a typical 2K acrylic/isocyanate system, the rheology controlagent may be incorporated with the acrylic polymer component which isthen blended with the isocyanate component just before application.

Application

The coating composition can be applied by conventional techniques, suchas, spraying, electrostatic spraying, dipping, brushing, and flowcoating. Spraying and electrostatic spraying are preferred methods ofapplication.

In OEM applications, the composition is typically baked at 60°-150° C.for about 15-30 minutes to form a coating about 25 to 75 microns thick.When the composition is used in a basecoat/clearcoat system, thebasecoat may be dried to a tack-free state and cured or preferably flashdried for a short period before the clearcoat is applied (wet-on-wet).The basecoat/clearcoat finish is then baked as mentioned above toprovide a dried and cured finish. The novel coating composition can alsobe formulated with the 3-wet (wet-on-wet-on-wet) coating process, wherethe primer, basecoat and clearcoat are applied to a substrate insequential steps without baking process in between each layer. The finalthree layer coated substrate coating is then baked to provide a driedand cure finish. The novel rheology control agent when formulated with acomposition containing a polyisocyanate crosslinking agent isparticularly useful in a non-baking refinish system, as will be readilyappreciated by those skilled in the art.

If used in refinishing vehicles, the base coat may be allowed to “dry tothe touch” at ambient temperature conditions or under warm air beforethe clear coating is applied. The base coating and clear coatingpreferably have a dry coating thickness ranging from 25 to 75 micronsand 25 to 100 microns, respectively. These coatings are usually cured atambient temperatures or at slightly elevated temperatures, such as, 40to 100° C.

The coating composition is particularly useful for the repairing andrefinishing of automobile bodies and truck bodies and parts, as a clearcoat, pigmented base coat, as a primer surfacer or primer filler. Thenovel composition has uses for coating any and all items manufacturedand painted by automobile sub-suppliers, frame rails, commercial trucksand truck bodies, including but not limited to beverage bottles, utilitybodies, ready mix concrete delivery vehicle bodies, waste haulingvehicle bodies, and fire and emergency vehicle bodies, as well as anypotential attachments or components to such truck bodies, buses, farmand construction equipment, truck caps and covers, commercial trailers,consumer trailers, recreational vehicles, including but not limited to,motor homes, campers, conversion vans, vans, large commercial aircraftand small pleasure aircraft, pleasure vehicles, such as, snow mobiles,all terrain vehicles, personal watercraft, motorcycles, and boats. Thenovel composition also can be used as a coating for industrial andcommercial new construction and maintenance thereof; cement and woodfloors; walls of commercial and residential structures, such as, officebuildings and homes; amusement park equipment; concrete surfaces, suchas parking lots and drive ways; asphalt and concrete road surface, woodsubstrates, marine surfaces; outdoor structures, such as bridges,towers; coil coating; railroad cars; printed circuit boards; machinery;OEM tools; signs; fiberglass structures; sporting goods; and sportingequipment.

The present invention is further defined in the following Examples. Itshould be understood that these Examples are given by way ofillustration only. From the above discussion and these Examples, oneskilled in the art can ascertain the essential characteristics of thisinvention, and without departing from the spirit and scope thereof, canmake various changes and modifications of the invention to adapt it tovarious uses and conditions. As a result, the present invention is notlimited by the illustrative examples set forth herein below, but ratheris defined by the claims contained herein below

The following Examples illustrate the invention. All parts andpercentages are on a weight basis unless otherwise indicated. Allmolecular weights disclosed herein are determined by LC/MS (LiquidChromatography/Mass Spectroscopy) and/or GPC (gel permeationchromatography) using a polystyrene standard.

EXAMPLES Example 1

The following show the preparation of rheology control agents:

General Preparation Procedure for Compounds Having Above Formulas(IV)-(XVI):

The aminoalcohol (4.16 mol) and chloroform (800 g) were charged into a 2L flask, under N₂ protection. The diisocyanate (0.42 mol) was added over2 hours at 0° C. into the flask with vigorous stirring, followed bycontinued stirring at RT (room temperature) for 2 hours. In most casesthe precipitation of a white solid was observed. The solid was purifiedthrough repeated filtration using acetonitrile as a wash solvent. Incases without solid precipitation addition of acetonitrile resulted insolid precipitation. The solid was dried under vacuum overnight at RT.In general LC/MS (Liquid Chromatography/Mass Spectroscopy) result showedpurity of >94% with small amounts of higher molecular weight impurities.

Under N₂ protection, the isolated white solid (0.26 mol) was added intoa 1000 ml flask followed by 500 g of N-methylpyrrolidone and heated at90° C., under stirring, to form a white suspension. Dibutyltin dilaurate(˜0.1% mole/mole) was added to this reaction mixture. Themono-isocyanate component (1 mol) was charged dropwise from an additionfunnel into the reaction mixture. The temperature of the reaction wasraised to 110° C. The reaction mixture becomes homogeneous. Aftercomplete addition the reaction mixture was maintained at 110° C. foradditional 2 hrs. After cooling to RT, the product is precipitated.

Compound Yield Aminoalcohol Diisocyanate (IV) 93.9% 2-(2-aminoethoxy)1,12 - ethanol diisocyanatododecane (V) 87.4% ethanol amine1,6-hexamethylene diisocyanate (VI) 90.1% 2-(2-aminoethoxy)1,4-diisocyanatobutane ethanol (VII) 84.3% 2-(2-aminoethoxy)1,6-hexamethylene ethanol diisocyanate (VIII) 67.0% 2-(2-aminoethoxy)1,8-diisocyanatooctane ethanol (IX) 76.4% 3-amino-1-propanol1,8-diisocyanatooctane (X) 87.1% ethanolamine 1,8-diisocyanatooctane(XI) 42.3% ethanolamine 1,5-diisocyanato-2- methyl pentane (XII) 86.6%3-amino-1-propanol 1,6-hexamethylene diisocyanate (XIII) 90.9%3-amino-1-propanol 1,4-diisocyanatobutane (XIV) 83.0% ethanolamine1,4-diisocyanatobutane (XV) 90.8% 3-amino-1-propanol 1,12-diisocyanatododecane (XVI) 93.2% ethanolamine 1,12- diisocyanatododecaneGeneral Preparation Procedure for Compounds Having Above Formulas(XXVI)-(XXIX):

The diamine 2-methyl-1,5-pentanediamine (3.0 g) was added into a 100 mlflask, then diluted with 100 ml CHCl₃. To this mixture was added 0.054mol monoisocyanate under constant agitation at R.T. After about 18 hrsof mixing at R.T. a clear and homogeneous reaction mixture was observed.The mixture was poured into ethyl ether and the obtained solids werefiltered and further rinsed with ethyl ether and dried under vacuum atR.T. A white solid was obtained. The product was analyzed using LC/MSspectroscopy.

Compound Isolated Yield Monoisocyanate (XXVI) 98% Pentyl isocyanate(XXVII) ~100% Dodecyl isocyanate (XXVIII) 96% Hexyl isocyanate (XXIX)~100% Octyl isocyanateGeneral Preparation Procedure for Compound Having Above Formula (XVII):

All operation is carried out under a dry N₂ atmosphere. Step 1:cyclohexyl isocyanate (0.11 mol) was added dropwise into a flaskcontaining ethanolamine (0.11 mol) and toluene at 0° C. At the end ofthe addition, the reaction mixture was allowed to warm up to roomtemperature and stir for 2 hours. The product is then collected bywashing with ether and dried in a vacuum oven at RT overnight. Thesample is then submitted for NMR and LC/MS analysis. Step 2: The productfrom step 1 is dissolved in 160 mL acetonitrile under N₂. The flask isthen heated in an oil bath at 70° C. with stirring. 48 mg ofdibutyltindilaurate is then added into the reaction mixture and the vialcontaining the catalyst was rinsed with a small amount of toluene toensure complete transfer of the catalyst. In the drybox, 13.78 g of HDI(hexamethylene diisocyanate) is mixed with 80 mL of acetonitrile andthen transferred into an addition funnel and added to the reactionmixture dropwise. At the end of the addition, the reaction temperatureis raised to 80° C. and stirred for another 4 hours. The reactionmixture is then cooled to room temperature and the solid is collected byfiltration and washed several times with acetonitrile. The product isthen dried in vacuum oven at room temperature overnight. Analysis byLC/MS confirms the formation of the product with a MW of 541.8, thecompound is essentially ˜100% pure.

General Preparation Procedure for Compounds Having Above Formulas(XXIII)-(XXIV):

75.0 g serinol and 400 g of chloroform plus ˜20 ml acetonitrile werecharged into a 500 ml flask, under N₂ protection and vigorous stirring.To this 13.85 g hexamethylene diamine diisocyanate was added drop bydrop (slowly) over 2 hrs. The flask was immersed into an ice bath duringthe addition. After the complete addition of hexamethylene diaminediisocyanate, a white precipitation is formed. The reaction wasmaintained at RT for one additional hour. The conversion was assessedusing LC/MS analysis indicating complete conversion of startingmaterials. The solid material was filtered with a medium size filterfollowed by repeated acetonitrile rinsing followed by repeated methanolrinsing. The solid was dried under vacuum overnight at RT. to obtain30.89 g of a white solid. The yield for this reaction is ˜100%.

In the next step 10.0 g of the dried product of the bis-urea tetraol wasadded into a 250 ml flask followed by 150 g of NMP. Under N₂ protection,the flask was immersed and stirred in an oil bath at 110° C. From adrybox, 0.171 mol of the monoisocyanate was transferred into anadditional funnel set on the top of the reaction flask. Next, 0.072 g ofDibutyltin dilaurate (Aldrich) was added into the reaction mixture, themonoisocyanate was added dropwise into the flask. After the addition of¼ of the monoisocyanate, the mixture became clear and homogeneous. Aftercomplete addition the reaction was maintained at 110° C. for additional3 hrs. LC/MS analysis indicates that all starting materials areconsumed. The mixture was dispersed and rinsed repeatedly usingacetonitrile. The white solid was filtered and dried under vacuo overnight.

Typical yields for these reactions are 88-95%.

Compound Monoisocyanate (XXIII) Hexyl isocyanate (XXIV) CyclohexylisocyanateGeneral Preparation Procedure for Compounds Having Above Formulas(XXX-XXXIII):

The following reaction was carried out under a blanket of nitrogen andvigorous stirring. 19.8 mmol of diacyl chloride in 10 mL of toluene wasadded dropwise into a flask containing 79.3 mmolN-octyl-N-(2-hydroxyethyl) urea and 1.76 g calcium hydroxide mixture in10 mL of 1M LiCl/NMP. The flask was held at about 5° C. during theaddition. The reaction mixture was allowed to warm to room temperatureand stirred for 4 hrs. The product was collected by filtration andsubsequently drying under vacuum. Typical yields for these reactions are50-95%.

Compound Diacyl chloride Monoisocyanate (XXX) Malonyl chloride Octylisocyanate (XXXI) Succinyl chloride Octyl isocyanate (XXXII) Adipoylchloride Octyl isocyanate (XXXIII) Glutaryl chloride Octyl isocyanateGeneral Preparation Procedure for Compounds Having Above Formulas(XXXIV-XXXV):

The following reaction was carried out under a blanket of nitrogen andvigorous stirring. 22.8 mmol of diacyl chloride in 10 mL of toluene wasadded dropwise into a flask containing 45.6 mmolN-cyclohexyl-N-(2-hydroxyethyl)urea and 1.76 g calcium hydroxide mixturein 90 mL of 1M NMP. The flask was held at about 5° C. during theaddition. The flask was equipped with a stirrer. The reaction mixturewas allowed to warm to room temperature and stirred for 4 hrs. Theproduct was collected by filtration and subsequently drying undervacuum. Typical yields for these reactions are 30-75%.

Compound Diacyl chloride Monoisocyanate (XXXIV) Adipoyl chlorideCyclohexyl isocyanate (XXXV) Succinyl chloride Cyclohexyl isocyanateGeneral Preparation Procedure for Compounds Having Above Formulas(XVIII-XXII):

The following reaction was carried out under a blanket of nitrogen andvigorous stirring. 0.15 mol of 1,6-diisocyanato hexane was addeddropwise into a flask containing 1.50 mol amino alcohol in 200 mL ofanhydrous chloroform. The flask was held at about 10° C. during theaddition. The reaction mixture was allowed to warm to room temperatureand stirred for overnight. The product was collected by filtration andsubsequently dried under vacuum to give a solid. Typical yields forthese reactions are over 90%.

The second step reaction was carried out under a blanket of nitrogen.68.8 mmol of acyl chloride in 10 mL of N-methyl pyrrolidone (NMP) wasadded dropwise into a flask containing 17.2 mmol of the aboveintermediate and 5.10 g calcium hydroxide in 48.3 mL of 1M LiCl/NMP. Theflask was held at about 5° C. during the addition. The flask wasequipped with a stirrer. The reaction mixture was allowed to warm toroom temperature and stirred overnight. The reactions were monitoredwith NMR analysis and the reaction was considered completion when thechemical shifts of protons and carbons that are adjacent to isocyanatedisappeared. The product was collected by filtration and subsequentlydried under vacuum. Typical yields for these reactions are over 50-90%.

Compound Acid chloride (XVIII) 2-Ethylhexanoyl chloride (XIX) Valerylchloride (XX) Isovaleryl chloride (XXI) t-Butylacetyl chloride (XXII)Palmitoyl chlorideGeneral Preparation Procedure for Compounds Having Above Formula(XLIII):

The following reaction was carried out under a blanket of nitrogen andvigorous stirring. 52.47 g (0.4 mol) L-leucine, 18.02 g (0.2 mol)diethylene glycol methyl ether, and 95.11 g (0.5 mol) p-toluenesulfonicacid were added to a 3-neck round bottom flask with a dean stark trapwith a reflux condenser on the top. 800 mL of dry benzene was added tothe mixture. The reaction temperature was maintained at 80° C. for 5hrs. 1.0 M NaHCO₃ solution was added into the stirred mixture slowlyuntil no bubbles were formed. After extraction, the organic layer wasdried over MgSO₄, followed by filtration. The product was subsequentlydried under vacuum to give a yellowish oil (56.52 g, 89.3% yield).

The second step reaction was carried out under a blanket of nitrogen andvigorous stirring. 7.92 g (51.0 mmol) of octylisocyanate in 20 mL oftoluene was added dropwise into a flask containing 9.02 g of the aboveintermediate mixture in 80 mL of toluene. The flask was held at about10° C. during the addition. The reaction mixture was allowed to warm toroom temperature and stirred overnight. The product was collected byfiltration and subsequently dried under vacuum to give a white powder(8.90 g, 94.7% yield).

General Preparation Procedure for Compounds Having Above Formula (XLIV):

The ethanol amine (4.16 mol) and chloroform (800 g) were charged into a2 L flask, under N₂ protection. The hexalene diisocyanate (0.42 mol) wasadded over 2 hours at 0° C. into the flask with vigorous stirring,followed by continued stirring at RT (room temperature) for 2 hours.Precipitation of a white solid was observed. The solid was purifiedthrough repeated filtration using acetonitrile as a wash solvent. Thesolid was dried under vacuum overnight at RT. LC/MS result showed purityof >94% with small amounts of higher molecular weight impurities.

In a 500 mL flask, 25.4 g (87.5 mmol) of above isolated white solid wasdissolved in NMP at 100° C., then 150.0 g (1.31 mol) of ε-caprolactonewas added. The temperature was then raised to 100° C. for 1 hr, then˜0.4 g of dibutyltin dilaurate was added. The reaction was maintainedfor ˜60 hrs at 110° C. Then the heating was withdrawn. The entiremixture remained as brownish liquid with increased viscosity. ˜419 g oforange color haze liquid was obtained. GPC analysis with THF andpolystyrene as standards confirmed the Mw ˜1,400. The calculated activesolid content was ˜29% (w/M_(n)).

Supporting Analytical Results

LC/MS (Liquid Chromatography/Mass Spectroscopy) analyses were performedon a Waters Alliance 2790 LC equipped with a MS (ESI) interface. Column:Zorbax SB-C18, 2.1×150 mm at 60° C.; Solvents: A=water+0.05% TFA,B=acetonitrile+0.05% TFA. Conditions: 95% A 0% A over 4.5 min, hold 3.5minutes, then return to initial conditions after 42 min; Wavelength: 220nm; Flow rate: 0.8 mL/min. NMR (Nuclei Magnetic Resonance) analyses wereperformed on a Bruker 500 MHz instrument. Solvents used to dissolve thesamples are A=DMSO-d6 (dimethyl sulfoxide), B=DMF-d7 (dimethylformamide), C=MeOD-d4 (methanol).

LC/MS NMR (ppm) Sample (M + 1) Solvent 1 H NMR (500 MHz) 13 C NMR (125MHz) IV 713.3 A 1.20(m); 1.25; 1.35(m); 24.89; 25.59; 26.76; 1.52(m);1.54(m); 1.65(m); 29.11; 29.28; 29.31; 1.67(m); 1.74(m); 1.76(m); 30.35;33.01; 50.01; 2.97(m): 3.02; 3.14(m); 63.34; 69.17; 70.58; 3.26(m);3.40(m); 3.55(m); 155.73; 158.54 4.04(m); 5.59(m); 5.67(m); 6.62 V 541.3A 1.11(m); 1.20(m); 1.25(m); 24.90; 25.58; 26.51; 1.36(m); 1.52(m);1.54(m); 30.30; 33.02; 39.57; 1.65(m); 1.67(m); 1.75(m); 39.83; 50.01;63.68; 1.92(m); 2.02; 2.17(m); 2.70; 155.78; 158.50 2.97(m); 3.02;3.19(m); 3.26(m); 3.91(m); 5.64(m); 5.70(m); 6.53 VI 601.3 A 1.12(m);1.21(m); 1.36(m); 24.83; 25.59; 27.96; 1.51(m); 1.54(m); 1.65(m); 32.98;39.75; 50.08; 1.67(m); 1.75(m); 1.77(m); 63.40; 69.23; 70.63; 2.88;2.99(m); 3.15(m); 155.76; 158.62 3.27(m); 3.42(m); 3.56(m); 4.04(m);5.52; 5.62; 6.43 VII 629.3 A 1.12(m); 1.21(m); 1.26; 24.83; 25.59;26.53; 1.37(m); 1.52(m); 1.66(m); 30.32; 32.98; 39.89; 1.76(m); 2.87;2.98(m); 50.09; 63.41; 69.24; 3.15(m); 3.28(m); 3.42(m); 70.64; 155.75;158.63 3.56(m); 4.05(m); 5.52; 5.60; 6.42 VIII 657.4 A 1.12(m); 1.21(m);1.25; 24.83; 25.59; 26.73; 1.37(m); 1.53(m); 1.66(m); 29.07; 30.34;32.98; 1.76(m); 2.87; 2.98(m); 50.08; 63.40; 69.23; 3.15(m); 3.28(m);3.42(m); 70.64; 155.90; 158.75 3.56(m); 4.05(m); 5.52; 5.59; 6.42 IX597.3 A 1.12(m); 1.21(m); 1.26; 24.84; 25.60; 26.73; 1.37(m); 1.52(m);1.66(m); 29.07; 30.36; 30.41; 1.75(m); 2.88; 2.98(m); 33.03; 37.04;39.95; 3.05(m); 3.27(m); 3.96(m); 50.04; 62.18; 155.91; 5.46; 5.52; 6.30158.67 X 569.3 A 1.12(m); 1.21(m); 1.26; 24.83; 25.59; 26.73; 1.37(m);1.52(m); 1.66(m); 29.06; 30.31; 33.00; 1.76(m); 2.88; 2.98(m); 39.68;39.99; 50.07; 3.20(m); 3.28(m); 3.93(m); 63.77; 155.82; 158.55 5.56;5.59; 6.32 XI 541.3 NA NA XII 569.3 A 1.12(m); 1.21(m); 1.26; 24.84;25.60; 26.53; 1.37(m); 1.52(m); 1.65(m); 30.34; 30.41; 33.03; 1.75(m);2.86; 2.98(m); 37.04; 39.90; 50.04; 3.05(m); 3.27(m); 3.95(m); 62.18;156.01; 158.66 5.47; 5.51; 6.29 XIII 597.3 A 1.20(m); 1.36; 1.53(m);24.83; 25.52; 27.89; 1.65(m); 1.75(m); 2.98; 3.03, 30.28; 32.98; 36.84;3.26(m); 3.95(m); 5.61; 6.52 39.59; 49.90; 61.99; 155.83; 158.52 XIV513.3 A 1.20(m); 1.36(m); 1.53(m); 24.90; 25.58; 27.92; 1.65(m);1.75(m); 2.98(m); 33.02; 39.56; 39.67; 3.02; 3.19(m); 3.27(m); 50.00;63.67; 155.77; 3.91(m); 5.65(m); 5.72(m); 158.49 6.55 XV 653.3 A1.18(m); 1.25; 1.36v(m); 24.90; 25.59; 26.76; 1.52(m); 1.64(m); 1.75(m);29.11; 29.27; 29.31; 2.97(m); 3.02; 3.25(m); 30.35; 30.37; 33.05;3.94(m); 5.56; 5.59; 6.50 36.90; 49.97; 62.07; 156.01; 158.59 XVI 625.3A 1.18(m); 1.25; 1.36(m); 24.90; 25.58; 26.76; 1.53(m); 1.66(m);1.75(m); 29.11; 29.28; 29.31; 2.97(m); 3.02; 3.19(m); 30.33; 33.02;39.55; 3.26(m); 3.91(m); 5.63(m); 39.87; 50.01; 63.68; 5.69(m); 6.52155.78; 158.49 XVIII N/A B 0.82(m); 1.24(m); 1.37(m); 11.35; 13.53;22.40; 1.51(m); 2.25(m); 3.03(m); 25.14; 29.20; 29.38; 3.30(m); 4.03(m);7.32(m); 29.53; 29.70; 29.87; 7.37(m) 31.41; 40.44; 46.86; 63.57;159.50; 175.60 XIX N/A B 1.02(m); 1.44(m); 1.54(m); 13.56; 22.15; 27.00;1.68(m); 2.52(m); 3.13(m); 33.65; 38.57; 63.95; 3.20(m); 3.50(m);4.18(m); 159.82; 173.49 7.58(m); 7.67(m) XX N/A B 1.05(m); 1.45(m);1.54(m); 22.13; 25.54; 26.99; 2.38(m); 3.13(m); 3.23(m); 38.60; 40.46;42.99; 3.50(m); 4.18(m); 7.60(m); 63.86; 159.83; 172.7. 7.67(m) XXI N/AB 0.95(m); 1.25(m); 1.35(m); 29.17; 35.45; 39.41; 2.20(m); 3.02(m);3.28(m); 47.17; 63.44; 159.57; 3.98(m); 4.34(m); 7.35(m); 171.78 7.43(m)XXIII 971.8 A 0.85(m); 1.25; 1.40; 2.69; 14.04; 22.29; 26.54; 2.97(m);3.02; 3.94; 5.60; 26.62; 28.88; 29.00; 5.79(m); 6.65 29.77; 30.24;31.53; 39.80; 40.94; 48.91; 63.82; 156.37; 157.91 XXIV 851.5 A 1.23(m);1.28; 1.37(m); 24.73; 24.88; 25.54; 1.53(m); 1.67(m); 1.76(m); 26.50;30.19; 32.98; 2.99(m); 3.14; 3.28(m); 3.95; 33.64; 39.80; 40.46;5.64(m); 5.84(m); 6.57 48.90; 50.09; 63.76; 155.67; 157.99 XXVI 343.3N/A N/A N/A XXVII 539.3 N/A N/A N/A XXVIII 371.4 A 0.80(m); 0.86(m);1.00(m); 6.16; 13.87; 14.87; 1.25; 1.34(m); 1.46(m); 17.58; 22.06;26.03; 2.77(m); 2.95(m); 3.32; 27.54; 29.99; 31.02; 5.71(m); 5.76(m)31.15; 33.26; 45.19; 57.23; 80.67; 158.07; 158.17;189.33 XXIX 427.3 N/AN/A N/A XXX N/A B 1.02(m); 1.41 (br); 1.55(m); N/A 3.13(m); 3.22(m);3.36(m); 3.63(m); 4.38(m); 5.87(m); 7.34(m); 7.51(m) XXXI N/A B 0.84(m);1.23(br); 1.38(m); N/A 2.69(s); 3.05(m); 3.17(m); 3.30(m); 3.46(m);4.02(m); 5.88(m); 7.28(m); 7.35(m) XXXII N/A B 1.01(m); 1.42(br);1.58(m); N/A 1.79(m); 2.57(m); 3.13(m); 3.23(m); 3.50(m); 4.18(m);4.34(m); 7.49(m); 7.56(m) XXXIII N/A B 0.84(m); 1.24(m); 1.38(m); N/A1.84(m); 2.42(m); 3.03(s); 3.31(m); 4.02(m); 4.15(m); 7.26(m); 7.38(m)XXXIV N/A B 1.36(m); 1.79(m); 2.57(s); 24.39; 24.78; 25.93; 3.13(m);3.48(m); 3.67(m); 33.66; 38.49; 48.13; 4.19(m); 7.46(m); 7.61(m) 63.98;159.08; 173.31 XXXV N/A B 1.35(m); 1.89(m); 2.89(s); 24.80; 25.78;3.13(m); 3.49(m); 3.67(m); 29.26;33.60; 38.39; 4.19(m); 7.45(m); 7.63(m)48.05; 64.27; 159.02; 172.47 XLIII 627.5 C 0.91(m); 0.96(m); 1.33(br);N/A 1.47(m); 1.57(m); 1.76(m); 3.11(m); 4.16(m); 4.30(m)

Example 2 Evaluation of Rheology Control Agents in Coating Compositions

The above prepared rheology control agents were tested for rheologicalactivity in a liquid organic resin coating composition. A high Tgacrylic resin (A), a hyperbranched polyester resin (B), and a low M.W.polyester resin (C) were used to evaluate these reagents. The organicresin systems were combined with 1-4% of the rheology control agent anddiluted with an indicated amount of solvent. After mixing vigorously,the mixture was checked for gelation/viscosity increase after certaintimes by inverting the container. The scale of the rheology activitytesting is based on a rating scale from 1-5:1=the content will flowimmediately, viscosity is the same as paint resin, 2=the content willflow immediately, but viscosity is higher than paint resin, 3=thecontent will flow between 2 to 10 seconds, 4=the content will flow after10 seconds, 5=mixture is not flowing at all. The results are shown inthe following Table 1:

TABLE 1 Gel Gel Compound Solid wt % Initial Gel Rating Rating Test(Rheology Resin Rheology Rating (5 after 2 after 24 Compositions Agent)Code LiCl % Agent min) hours hours 1 XIX A 1.2 2.0% 1 2 2 2 XIX C 1.22.0% 1 4 4 3 XX A 1.5 2.0% 1 4 4 4 XX C 1.5 2.0% 2 3 3 5 XXI A 1.5 2.0%1 2 2 6 XXII A 1.5 2.0% 1 2 2 7 XXII C 1.5 2.0% 1 1 2 8 XXIII A 0 2.0% 22 2 9 XXX A 2.5 2.0% 2 2 2 10 XXIX B 2.1 2.0% 1 2 2 11 XXXI A 2.5 2.0% 23 2 12 XXXI B 2.5 2.0% 2 2 2 13 XXXII B 2.5 2.0% 1 1 3 14 XXXIII A 2.32.0% 5 5 5 15 XXXIII B 2.3 2.0% 3 4 5 16 XXXII A 2.5 2.0% 1 4 5 17 XXXVA 2.3 2.0% 1 2 2 18 XXXV B 2.3 2.0% 1 2 2 19 XLIII A 2.1 1.0% 3 4 4 20XLIII B 2.1 1.0% 1 5 5 *the amount of resin used in each case is 5.0 g.

The above gel rating results show that a small amount (1-4% by wt.) ofthe rheology control agents of this invention are able to thickencoating compositions containing conventional binders used in coatingcompositions.

The following Table 2 shows gel test results where compositions wereevaluated of a high Tg (glass transition temperature) acrylic resin Aand a hyperbranched polyester resin B with rheology control agents ofthis invention in the presence 3% by wt. of LiCl.

TABLE 2 Resin A Resin B Test SCA % in SCA % SCA % Composition CompoundLiCl/NMP LiCl % Time Gel Time Gel 21 (XIV) 42.2% 3.0% 2.0% 13′00″ 2.0%5′00″ 22 (XIII) 16.6% 3.0% 2.0% 1′30″ 2.0% 1′10″ 23 (V) 25.0% 3.0% 2.0%4′10″ 2.0% 3′10″ 24 (XII) 18.5% 3.0% 2.0% 1′30″ 2.0% 50″ 25 (VII) 36.8%3.0% 2.0% ~15 hrs 2.0% ~10 hrs 26 (X) 17.1% 3.0% 2.0% 2′30″ 2.0% 2′00″27 (IX) 18.2% 3.0% 2.0% 50″ 2.0% 45″ 28 (VIII) 37.0% 3.0% 2.0% 10′00″2.0% 8′30″ 29 (XV) 20.7% 3.0% 2.0% 20″ 2.0% 1′20″ 30 (XVI) 13.1% 3.0%2.0% 12″ 2.0% Not Gel 31 (IV) 29.2% 3.0% 2.0% 35″ 2.0% 20″ 32 (XXIII)35.1% 3.0% 2.0% 30″ 2.0% 1′10″ 33 (XIV) 25.0% 3.0% 2.0% 8′00″ 2.0%5′00″ * SCA % in LiCl/NMP is the solid weight % of rheology controlagent in the LiCl/NMP solution; LiCl % is the solid weight % of LiCl inthe LiCl/NMP solution. SCA % is the weight % of rheology control agentin overall solid binder resin.

The above test results shown in Table 2 show that 2 wt % of the rheologycontrol agent in this invention thicken binder resin such as resins Aand B effectively. Gel activity depends on the structure of a rheologycontrol agent and the resin used in the composition that is beingtested. Although compound (XVI) did not gel resin B (hyperbranchedpolyester resin), it did increase the viscosity of the composition.

The examples in Table 3 were prepared by incorporating the examplecompound at 50° C. into methylamyl ketone, this dispersion was added tothe resin, in this case resin B. The mixture was agitated under shear tothe elevated temperature (˜40-50° C.). After this, the sample wasallowed to cool down to RT under continued shear. Sample composition:1.0 wt % example compound in total resin solid at 45.0 wt % total solidin wet sample.

TABLE 3 Brookfield ratio Test of shear rates: 0.5 Composition CompoundSCA% rpm/150 rpm 34 (XXVI) 1.0% 8.1 35 (XXIII) 1.0% 9.2 36 (XXIV) 1.0%13.9 37 (XXII) 1.0% 17.5 38 (XXXV) 1.0% 3.2 39 (XXXII) 1.0% 7.9 40(XXXIII) 1.0% 3.1 41 (XXXI) 1.0% 4.7 SCA% is the solid weight % ofrheology control agent in overall binder resin.

The brookfield ratio (floc index) indicates that these examplesdemonstrated shear thinning properties with high viscosity at low shearrate and low viscosity at high shear rate.

The results in Tables 1-3 indicate that the addition of the rheologycontrol additives of this invention, even at these low levels, totypical binder resin systems results in the formation of a gel or asolution with increased viscosity and therefore, changes the rheologicalbehavior of these systems dramatically. In Table 3 the change of theobserved viscosity at different shear ratios also supports the proposedrheological modification of the binder resin.

Example 3

The following lacquer base coating composition was prepared:

Pigment Dispersion #1 Preparation:

Add the Following in Order with Mixing: Grams

Highly Branched Copolyester Polyol* 58.68

Methyl Amyl ketone 138.38

Add slowly with mixing at high speed (approximately 5000 RPM) on a labtop high speed disperser using a blade with a diameter of approximately6 cm.

Rheology control agent 17.5

Structure X (16.8% in NMP With 3% LiCl)

Mix at high speed (approximately 5000 RPM) on a lab top high speeddisperser, using a blade with a diameter of approximately 6 cm, for 30minutes. *Same composition as Solution 5 of WO 03/070843 but made inmethyl amyl ketone as the solvent vs. propylene glycol monomethyl etheracetate.Base Coating Composition Preparation:

Solvent Blend A Component Grams Acetone 162 Isobutyl alcohol 234Isopropanol 180 Methyl isobutyl ketone 108 Aliphatic hydrocarbon (bp =90-110 C.) 270 Xylene 216 Aromatic hydrocarbon (bp = 150-190 C.) 18Total 1188

Solvent Blend B Component Grams Butyl acetate 7964.60 Methyl amyl ketone3413.40 Total 11378.00

A CAB Solution, shown below, was produced by slowly adding celluloseacetate butyrate to solvent while mixing on an air mixer:

Component Description Grams Solvent Blend B Solvent Blend 5055.57CAB-381-2** cellulose acetate butyrate 669.12 CAB-531-1** celluloseacetate butyrate 223.04 Total 5947.73 **Supplied by Eastman ChemicalCo., Kingsport, Tennessee.

Silver Metallic Tinting Composition Grams Acrylic resin*** 46.02 SparkleSilver 5745 Aluminum Paste from Silberline 25.47 Solvent blend A 24.91Total 96.4 ***A random acrylic copolymer Sty/IBOMA/EHA/HEMA/BMA/MMA(10/10/15/30/10/25% by weight) at 66.40% wt solids in n-butyl acetatewas prepared with the standard free radical polymerization procedure.(Sty—styrene, IBOMA—isobutyl methacrylate, EHA—2-ethyl hexyl acrylate,HEMA—hydroxy ethyl methacrylate, BMA—butyl methacrylate, MMA—methylmethacrylate)

A lacquer base coating composition was made by adding the componentslisted in Table 4 in the order shown and mixed using an air mixer.

TABLE 4 Component Parts by Weight Pigment Dispersion #1 (prepared above)214.56 Graft acrylic copolymer prepared in accordance with 2.82 theprocedure described in Example #6 of U.S. Pat. No. 6,472,463 but usingmethyl tol sulfonate versus benzyl chloride Acrylic resin (describedabove) 9.20 Graft copolymer (Example #1 of U.S. Ser. 79.70 No.10/983,462) CAB solution (prepared above) 152.78 Silver Metallic TintingComposition (prepared above) 96.40 Solvent Blend A (prepared above)244.54 Total 800.00

Panel Preparation

The silver basecoats were sprayed per the application instructions usedfor DuPont ChromaPremier® Basecoat specified in the DuPont ChromaSystem®Tech Manual. The basecoats were sprayed to hiding over ACT APR10288 coldrolled steel panels which were wiped with DuPont First Klean® 3900Ssanded with 80 grit sand paper, wiped again with DuPont First Klean®3900S, then primed with DuPont Variprime® 615S/625S Self-Etching Primeras per the instructions in the DuPont ChromaSystem® Tech Manual. Thebasecoats were clearcoated with DuPont ChromaClear® V-7500S Multi-Use asper the instructions in the DuPont ChromaSystem® Tech Manual.Basecoat/clearcoat panels were flashed and then baked in a 140° F. ovenfor 30 minutes. Topcoated panels were allowed to air dry for anadditional 7 days prior to testing.

Below are the color readings recorded by a DuPont ChromaVision CustomColor MA 100B meter manufactured by X-Rite, Inc. of Grandville, Mich.:

Test Results

Below in Table 5 are the Head-on-Brightness (HOB) and flop values forthis base coating composition:

TABLE 5 Near spec Base Coating Composition Lightness HOB Flop Preparedabove 121.9 6.32

This data shows that the use of the rheology control agent of thisinvention gave exception flake control in a refinish lacquer basecoat.This coating contains 2% on binder of the rheology control agent. Thislevel of rheology control agent is much lower than the typical level oftraditional rheology control agents such as wax which are used at around10% on binder in these types of coatings. Thus the rheology controlagents of this invention give excellent coating appearance at m

Example 4

The above prepared rheology control agents were tested for rheologicalactivity in a waterborne based coating composition, Aquacryl® 514,described in U.S. Pat. No. 6,204,319. Each of the waterborne coatingcompositions was blended with 5% of various rheology control agents anddiluted with an appropriate amount of aqueous carrier. After mixingvigorously, the mixture was checked for gelation/viscosity increaseafter certain times by inverting the container.

The results on various rheology control agents are shown in followingTable 6:

TABLE 6 Rheology Control Agents RCA Soild wt % Gel time (hh:mm:ss) V 524:00:00 VI 5 00:00:30 VII 5  0:02:00 XVII 5  0:10:00 XXIX 5 viscous XXX5 viscous XL 5 viscous XLIV 5 24:00:00 LII 5 viscous LIII 5 viscous

The above test results shown in Table 6 show that 5 wt % of the rheologycontrol agent of this invention thickens a water borne coatingcomposition effectively. Gel activity depends on the structure of arheology control agent and the resin used in the aqueous coatingcomposition.

Example 5

The above prepared rheology control agents V, VI and L were tested forrheological activity in a waterborne based coating using a BrookfieldViscometer. The waterborne coating composition described in Example 4was combined with 5% of the rheology control agent and diluted with anappropriate amount of aqueous carrier. After mixing vigorously, theviscosity profile was obtained for each sample and the data was fit to apower law equation below. K and n are used to determine the shearthinning properties.η=Kγ&^(n−1)log η=(n−1)log γ&+log KThe results are shown in the following Table 7:

TABLE 7 Rheology RCA Soild Control Agents wt % K desc (Pa · s^(n)) ndesc V 5 1.46 0.29 VI 5 0.54 0.44 L 10 3.92 0.43

The brookfield data indicates that these examples demonstrated shearthinning properties with high viscosity at low shear rate and lowviscosity at high shear rate.

The results in Tables 6 and 7 shows that the addition of the rheologycontrol additives of this invention, even at these low levels, totypical aqueous coating composition results in the formation of a gel ora solution with increased viscosity and therefore, changes therheological behavior of these coating compositions dramatically. Table 7shows the change of the viscosity at different shear ratios whichsupports the rheological modification of water-borne coatingcompositions.

1. A rheology control agent for coating compositions, comprising: acompound having the formula (II) including isomers or mixtures ofisomers thereof:

wherein R is a C3 to C16 linear or branched alkylene group, a C1 to C6linear or branched alkylene group bearing a C5-C16 cycloaliphatic group,a C5-C16 cycloaliphatic or alkyl substituted cycloaliphatic group, R⁹ isa C1 to C8 linear or branched alkylene group, a —(CH₂CH₂—O)_(n)—CH₂CH₂—group with n being 1 to 4, and R¹⁰ is a C3 to C16 linear or branched,alkylene group linkage; wherein n=1-7, m=1-7.
 2. The rheology controlagent of claim 1 having the following formula

(XLIV) wherein n=1-7, m=1-7.
 3. A solvent-borne coating compositioncomprising a binder of a film forming polymer and the rheology controlagent of claim
 1. 4. The solvent-borne coating composition of claim 3comprising 5 to 95 percent by weight of an organic solvent, based on theweight of the coating composition and 5 to 95 percent by weight, basedon the weight of the coating composition of film forming binder and 0.01to 30 percent by weight, based on the weight of the binder, of therheology control agent.
 5. The solvent-borne coating composition ofclaim 4 containing pigment.
 6. The solvent-borne coating composition ofclaim 4 wherein the film forming polymer comprises linearpoly(meth)acrylates, branched, grafted or segmented poly(meth)acrylates,polyesters, polyesterurethanes, polyepoxides or any mixtures thereof. 7.The solvent-borne coating composition of claim 6 containing acrosslinking agent selected from the group of a polyisocyanate, analkylated melamine, polyepoxide and any mixtures thereof.
 8. Thesolvent-borne coating composition of claim 4 containing 0.1 to 10percent by weight, based on the weight of the binder, of the rheologycontrol agent.
 9. The solvent-borne coating composition of claim 4containing silica in a weight ratio of rheology control agent to silicaof 0.1:1.0 to 1.0:0.1.
 10. A substrate coated with at least one driedlayer of the composition of claim
 3. 11. An automotive body coated withat least one dried layer of the composition of claim
 3. 12. Awater-borne coating composition comprising a binder of a film formingpolymer and the rheology control agent of claim
 1. 13. The water-bornecoating composition of claim 12 comprising 5 to 95 percent by weight ofan aqueous carrier, based on the weight of the coating composition and 5to 95 percent by weight, based on the weight of the coating compositionof film forming binder and 0.01 to 30 percent by weight, based on theweight of the binder, of the rheology control agent.
 14. The water-bornecoating composition of claim 12 containing pigment.
 15. The water-bornecoating composition of claim 12 wherein the film forming polymercomprises linear poly(meth)acrylates, branched, grafted or segmentedpoly(meth)acrylates, polyesters, polyesterurethanes, polyepoxides or anymixtures thereof.
 16. The water-borne coating composition of claim 15containing a crosslinking agent selected from the group of apolyisocyanate, an alkylated melamine, polyepoxide and any mixturesthereof.
 17. The water-borne coating composition of claim 12 containing0.1 to 10 percent by weight, based on the weight of the binder, of therheology control agent.
 18. The water-borne coating composition of claim12 containing silica in a weight ratio of rheology control agent tosilica of 0.1:1.0 to 1.0:0.1.
 19. A substrate coated with at least onedried layer of the composition of claim
 12. 20. An automotive bodycoated with at least one dried layer of the composition of claim 12.